Stanislav V. Vassilev, David Baxter, Lars K. Andersen, Christina G. Vassileva

Fuel 105 (2013) 4076
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Fuel
journal homepage: www.elsevier.com/locate/fuel
Review article
An overview of the composition and application of biomass ash. Part 1.

Phasemineral and chemical composition and classication
Stanislav V. Vassilev a,b,, David Baxter a, Lars K. Andersen a, Christina G. Vassileva b
a
b
Institute for Energy and Transport, Joint Research Centre, European Commission, P.O. Box 2, NL-1755 ZG Petten, The Netherlands
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Soa 1113, Bulgaria
a r t i c l e
i n f o
Article history:
Received 18 July 2012
Received in revised form 13 September
2012
Accepted 17 September 2012
Available online 4 October 2012
Keywords:
Biomass ash
Phase and mineral composition
Chemical composition
Classication
a b s t r a c t
An extended overview of the phasemineral and chemical composition and classication of biomass ash
(BA) was conducted. Some general considerations related to the composition of BA and particularly problems associated with this issue were discussed initially. Then, reference peer-reviewed data including
phasemineral composition and properties of BAs plus own investigations were used to describe and
organise the BA system. It was found that BA is a complex inorganicorganic mixture with polycomponent, heterogeneous and variable composition. The phasemineral composition of BA includes: (1)
mostly inorganic matter composed of non-crystalline (amorphous) and crystalline to semi-crystalline
(mineral) constituents; (2) subordinately organic matter consisting of char and organic minerals; and
(3) some uid matter comprising moisture and gas and gasliquid inclusions associated with both inorganic and organic matter. Approximately 229 forming, major, minor or accessory phases or minerals were
identied in BA. These species have primary, secondary or tertiary origin in the combustion residue and
they are generated from natural (authigenic and detrital) and technogenic phases or minerals originally
present in biomass. Common topics related to BA such as: terminology clarication; chemical composition; contents and concentration trends; correlations and associations; formation and behaviour; fusion
temperatures; and leaching; were discussed and compared to coal ash. A general characterization of the
phasemineral composition and description of the occurrence and origin for common constituents in BA,
namely: (1) silicates; (2) oxides and hydroxides; (3) sulphates (plus sulphides, sulphosalts, sulphites and
thiosulphates); (4) phosphates; (5) carbonates (plus bicarbonates); (6) chlorides (plus chlorites and chlorates); (7) nitrates; (8) glass; (9) other inorganic phases; (10) organic phases; and (11) organic minerals;
were also conducted and compared to coal ash. Finally, certain major associations related to the occurrence, content and origin of elements and phases were identied in the BA system and they include:
(1) SiAlFeNaTi (mostly glass, silicates and oxyhydroxides); (2) CaMgMn (commonly carbonates,
oxyhydroxides, glass, silicates and some phosphates and sulphates); and (3) KPSCl (normally phosphates, sulphates, chlorides, glass and some silicates and carbonates). It was found that these systematic
associations in BA have a key importance in both fundamental and applied aspects, namely their potential application for classication and indicator purposes connected with innovative and sustainable processing of BA. The potential utilization, technological and environmental advantages and challenges
related to BA using the above classication approach are described in Part 2 of the present work.
2012 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
General considerations about biomass composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Common issues concerning the composition of biomass ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Materials, methods and data used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Common observations about biomass ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
42
43
48
51
51
Corresponding author at: Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Soa 1113, Bulgaria. Tel.: +359
2 9797055; fax: +359 2 9797056.
E-mail address: vassilev_stan@yahoo.com (S.V. Vassilev).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.09.041
S.V. Vassilev et al. / Fuel 105 (2013) 4076
4.
3.1.1.
Definition, specification and terminology clarification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.3.
Content and concentration trend. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.4.
Correlation and association . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.5.
Formation and behaviour . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.6.
Fusion temperatures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.7.
Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.7.1.
Water leaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.7.2.
Leaching by different solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.7.3.
Sequential leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
General comments about phasemineral composition of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Phasemineral composition of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.1.
Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.2.
Oxides and hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.3.
Sulphates, sulphides, sulphosalts, sulphites and thiosulphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.4.
Phosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.5.
Carbonates and bicarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.6.
Chlorides, chlorites and chlorates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.7.
Nitrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.8.
Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.9.
Other inorganic phases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.10.
Organic phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.11.
Organic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Chemical and phasemineral classifications of biomass and biomass ash and their potential applications . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
51
51
52
54
54
57
62
62
62
63
65
65
67
68
68
68
68
69
69
69
69
70
70
70
72
73
73
Nomenclature
A
AFT
BA
BC
CC
Daf
DAI
Db
DT
DTA
DWR
EDF
FC
FT
HT
HTA
ICP
LA
ash yield
ash-fusion temperature
biomass ash
beech wood chips
corn cobs
dry, ash-free basis
SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2/
CaO + MgO + MnO + K2O + P2O5 + SO3
dry basis
initial deformation temperature
differential-thermal analysis
dry water-soluble residue
enrichment/depletion factor
xed carbon
uid temperature
hemispherical temperature
high-temperature ash (>500 C)
inductively coupled plasma
laser ablation
1. Introduction
It is widely accepted that biofuels combustion does not contribute to the greenhouse effect due to the CO2 neutral conversion
thanks to the renewability of biomass. The focus on bioenergy as
an alternative to fossil energy has increased tremendously in recent times because of global warming problems originating mostly
from fossil fuels combustion. Therefore, extensive investigations
have been carried out worldwide recently to enhance biomass
use instead of fossil fuels for energy conversion ([1,2] and references therein).
The global growth of biomass is estimated between 112 and
220 billion tonnes per year [38]. However, the annual world production of biomass with potential energy application at present is
LTA
M
MA
MM
MS
OM
PP
R2
RH
SG
SS
SSA
ST
TGA
VM
WS
XRD
%
low-temperature ash (100250 C)

moisture
medium acid
marine macroalgae
mass spectrometry
organic matter
plum pits
correlation coefcient
rice husks
switchgrass
sunower shells
specic surface area
spherical temperature
thermo-gravimetric analysis
volatile matter
walnut shells
X-ray powder diffraction
weight%
estimated to be about 3 billion tonnes for forest residues [9], between 1.1 and 3.1 billion tonnes for agricultural residues [911],
about 1.1 billion tonnes for municipal solid wastes [3] plus sewage
sludge and other biomass resources [9,12]. Biomass currently contributes between 8% and 15% of the world energy supplies as heat,
electricity and fuels for transportation [5,8,9,1318]. By 2050, up to
3350% of the worlds current primary energy consumption could
be met by biomass [3,8,18,19]. In total about 9597% of the worlds
bioenergy is produced by direct combustion of biomass [16,2022].
Hence, approximately 476 million tonnes of biomass ash (BA) may
be generated worldwide annually if the burned biomass is assumed to be 7 billion tonnes with 6.8% mean ash yield on dry
basis [1]. This quantity is comparable to that of coal ash,
namely 780 million tonnes produced per year at present [23]. The
42
perspective of increasing large-scale combustion of natural biomass and its co-combustion with semi-biomass (contaminated
biomass such as municipal solid waste, refuse-derived fuel, sewage
sludge, demolition wood and other industrial organic wastes) and
solid fossil fuels (coal, peat, petroleum coke) seems to be one of the
main drivers for biofuel promotion by many countries worldwide
in the near future. Therefore, some of the major open questions related to extensive biomass combustion are what we are going to do
with this huge amount of BA and if there are any environmental
risks related to BA. The present overview will cover such topics.
biomass and BA dene properties, quality and application perspectives, as well as technological and environmental problems or
advantages related to any fuel and its products [1,2].
As rst and second steps, two extended overviews of the bulk
chemical composition [1] and organic and inorganic phase composition [2] of biomass, respectively, were conducted recently. Extensive reference peer-reviewed data for numerous biomass varieties
(86 for chemical composition and 93 for phase composition) plus
own investigations of eight varieties of biomass were used to describe the composition of the biomass system. In these previous
overviews it was found that:
1.1. General considerations about biomass composition

Two fundamental aspects related to the use of BA are:
(1) To extend and improve the basic knowledge on composition
and properties and
(2) To apply this knowledge for the most innovative and sustainable utilization and/or an environmentally safe disposal.
The composition of BA depends on various factors; however, it
is directly related to the biomass used as feedstock because the original constituents in biomass are the precursors for the newly
formed components in BA (Tables 1 and 2). Therefore, detailed
knowledge of the biomass composition is also required for the reliable characterization of BA. The systematic identication, quantication and characterization of chemical and phase composition of a
given solid fuel and its conversion products are the initial and most
important steps for their proper utilization. The composition of
(1) Biomass, similar to solid fossil fuels, is a complex heterogeneous mixture of organic matter and, to a lesser extent, inorganic matter, containing various intimately associated solid
and uid phases with different contents and origin. The
phases in biomass originate from natural (authigenic and
detrital) and anthropogenic (technogenic) processes during
pre-syngenesis, syngenesis, epigenesis and post-epigenesis
of biomass according to the main formation process and
place, time and mechanism of phase formation. The main
structural organic components in biomass are cellulose,
hemicellulose and lignin and these matrices contain in addition various major, minor or accessory organic and inorganic
phases.
(2) The chemical and phase differences among the specied natural and anthropogenic biomass groups and sub-groups are
signicant and they are related to diverse biomass source
and origin, namely from plant, animal and manufactured
Table 1
Phase composition of biomass ash.
Matter
State and type of constituent
Phase, mineral and particle morphology
Inorganic matter
Solid, non-crystalline
(amorphous)
(amorphous)
Solid, crystalline to semicrystalline (mineral)
Spherical and spheroidal glass particles (massive, vesicular, cenospheres, plerospheres, dermaspheres,
ferrospheres, ferrispheres, others)
Angular, irregular and other aspherical glass particles (massive, hollow, vesicular, bres, needles, cylinders,
discs, slabs, sheets, lacy, spongy, porous, elongated, rounded, agglomerates, others)
Crystals, grains, aggregates, clusters, ferrospheres, ferrispheres, skeletal spheres and spheroids,
agglomerates and others of various minerals or poorly crystallized mineraloids (silicates, oxides and
hydroxides, sulphates, sulphides, sulphosalts, sulphites, thiosulphates, phosphates, carbonates, chlorides,
chlorites, chlorates, nitrates, native elements, pure metals, metallic alloys, others)
Organic matter
Solid, crystalline (mineral)

(amorphous) to semi-crystalline
Crystals, grains and aggregates of organic minerals (whewellite-weddelite and other groups)
Char including semi-coked, coked, soot and tar particles (angular, irregular, rounded, massive, hollow,
vesicular, spongy, porous, skeleton, needles, whiskers, bres, scaly, aky, sheets, clusters of rosettes,
cylinders, discs, slabs, spherical, spheroidal, agglomerates, others)
Fluid matter
Fluid, liquid, gas
Moisture and gas and gasliquid inclusions associated with both inorganic and organic matter
Table 2
Origin of phases in biomass ash.
Origin
Formation
process
Place of formation
Time of formation
Formation mechanism
Primary
Natural
Biomass
Original phases or minerals that have undergone no phase transformations during

combustion
Secondary
Anthropogenic
(technogenic)
Combustion
installation
Before and during plant

growing, and after plant
died
During combustion
Tertiary
Natural
Transportation
facility and
disposal site
During transport and

storage of combustion
residues
New phases generated by solid, liquid and gas reactions among pre-existing and
newly formed compounds (amorphization, carbonation, carbonization, coalescence,
crystallization, decarbonation, decomposition, dehydration, dehydroxylation,
destruction, desulphation, dissolution, evaporation, fragmentation, hydration,
hydroxylation, melting, nucleation, oxidation, polymorphic transformation,
precipitation, recrystallization, reduction, softening, solid-state reactions,
sulphation, vitrication, volatilization, combined conversions, others)
New minerals or phases originated by wheathering (amorphization, carbonation,
crystallization, decarbonation, decomposition, dehydration, dehydroxylation,
destruction, desulphation, dissolution, evaporation, hydration, hydroxylation,
oxidation, polymorphic transformation, precipitation, recrystallization, solid-state
reactions, sulphation, vitrication, others)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
products. The composition of semi-biomass is more complex

and quite complicated compared with natural biomass as a
result of incorporation of various non-biomass materials
through processing steps.
Biomass has highly variable composition and properties,
especially with respect to moisture, structural components
and inorganic constituents. These characteristics are more
changeable and differ signicantly in comparison with those
of coal and a good understanding is critical for proper use of
biomass and/or co-processing with coal and other fuels. The
major and minor elements in biomass, in decreasing order of
abundance, are commonly C, O, H, N, Ca, K, Si, Mg, Al, S, Fe, P,
Cl and Na, plus Mn, Ti and other trace elements. In comparison with coal, natural biomass is normally: (1) highly
enriched in Mn > K > P > Cl > Ca > (Mg, Na) > O > moisture >
volatile matter; (2) slightly enriched in H; and (3) depleted
in ash, Al, C, Fe, N, S, Si and Ti.
The organic matter (5499%, mean 93%, on dry basis) in biomass has: non-crystalline character and only limited crystallinity with larger d-spacings (between 0.33 and 0.88 nm) in
comparison with carbonised fuels such as coal, char and
coke (between 0.26 and 0.59 nm); and characteristic intermolecular distances at about 0.59 nm and 0.40 nm related
to complex cellulose hemicellulose lignin oxalate
opal associations.
The structural components in biomass belong to six orders
(or types) as the most common orders include: cellulose > hemicellulose > lignin; cellulose > lignin > hemicellulose; and hemicellulose > lignin > cellulose. Hemicellulose
tends to be abundant in annual and fast-growing plants or
plant parts and this constituent plays a role of conducting
and concentrating tissue for mineralized solutions abundant
in sulphates, chlorides, nitrates and silicic acid in plants. Cellulose, lignin and extractives show associations with different non-mobile and mobile elements in biomass.
Bulk extractives (187%, mean 10%, on dry, ash-free basis) in
biomass consist of various organic and inorganic components and their contents are normally higher in herbaceous
and agricultural biomass than in wood and woody biomass.
The uid matter (363%, mean 14%, normally on as received
and air-dried basis) in biomass is a mineralized aqueous
solution associated with both inorganic and organic matter.
These water solutions have slightly acidic to neutral character with salty, sea salty to brine total mineralization and variable electrical conductivity. These three characteristics
correlate positively with one another and commonly with
inorganic matter and mobile S, Cl, Na and N components.
The inorganic matter (0.146%, mean 7%, on dry basis) in
biomass includes various minor and accessory mineral species and poorly crystallized mineraloids from various mineral groups and classes, as well as some amorphous
inorganic phases. The most mobile water-soluble phases in
biomass are chlorides, sulphates, oxalates and nitrates plus
some carbonates and amorphous material with both organic
and inorganic character.
Certain major associations related to the occurrence, content
and origin of elements and phases were identied in natural
biomass and they include: (1) CH (mainly as authigenic cellulose, hemicellulose, lignin and organic extractives); (2) Si
AlFeNaTi (mostly as detrital silicates and oxyhydroxides,
excluding authigenic opal); (3) CaMgMn (commonly as
authigenic oxalates and carbonates); and (4) NKSPCl
(normally as authigenic phosphates, sulphates, chlorides
and nitrates). These systematic associations are important in
both fundamental and applied aspects, namely their potential
43
application for classications and indicator purposes connected with innovative and sustainable processing of
biomass.
(10) The occurrence, content, origin and association of different
inorganic matter types and mineral classes, groups and specic species are likely to be the major reasons for many technological problems (combustion efciency, low-temperature
eutectics, agglomeration, slagging, fouling, corrosion, abrasion-erosion, partitioning, ash utilization) and environmental concerns (water, soil and plant contamination, leaching,
alkalinity, emission, inhalation, ash disposal) during biomass
processing (see below and Part 2).
(11) Biomass ashes (500 C) have highly crystalline character
with limited occurrence of inorganic amorphous material
and organic matter. Various species of carbonates, sulphates,
silicates and phosphates were identied in these ashes and
most of them are newly formed minerals during biomass
combustion.
(12) Energy from biomass cannot only be carbonneutral, but
carbon-capture and storage is also possible due to xation
of CO2 in the combustion residues as newly formed carbonates. Some biomass is highly enriched in alkaline-earth and
alkaline constituents (see below and Part 2) and this favourable composition can contribute signicantly to the capture
of volatile C, S, Cl and trace elements in combustion residues.
Hence, there are potential possibilities for reduction of
harmful emissions by modication of the feed fuel composition through tailored and self-cleaning fuel mixtures during
co-ring or co-gasication of biomass with fossil fuels.
Both previous overviews concluded that future detailed and
systematized data on the phasemineral composition of BA are required as a third step to explain some leading trends and associations connected with biomass and its conversion products.
Therefore, the main purposes of this subsequent work presented
here are: (1) to perform an overview of the chemical and especially
phase composition of BAs and (2) to indicate the potential applications of BAs based on the composition and properties of these combustion products.
1.2. Common issues concerning the composition of biomass ash
A detailed review of the scientic literature, including more
than 600 mostly peer-reviewed references and data compilations
has been conducted to systematise the results obtained for composition and properties of biomass and BA. It was found that numerous studies on phase composition of BA have been performed
worldwide and data for ashes of different biomass varieties have
been generated and published [10,13,14,18,24141]. As a result,
signicant information for inorganic matter (various phases and/
or minerals) and, to a lesser extent, organic matter (char, others)
identied in BA has been collected and arranged systematically
(Table 3). These results provide a sound foundation for an initial
database that can be used for phase characterization and subsequent classication and sustainable exploitation of BA. It was also
found that serious problems related to phase investigations of BA
occur and some of them are similar to those determined for chemical and phase studies of biomass [1,2]. Therefore, an attempt to
summarize the problems related to phase investigations of BA
was initially undertaken and is described below:
(1) There is a huge amount of data on the phase composition of
BA on the Internet and numerous scientic reports from projects, conference proceedings and workshop presentations,
as well as in many publications; however, such information
is unreliable because the data are not peer-reviewed.
44
Table 3
Phases and minerals identied in biomass ashes.
Phase, mineral
1. Inorganic matter
1.1. Silicates
Afwillite
Akermanite
Albite
Amorphous silica
Anorthite
Augite
Bredigite
Ca aluminosilicates
Ca chlorosilicate
CaFeMg silicate
CaMg silicates
Ca silicate hydrate
Ca silicates
Cd silicate
Chlorite
Clay minerals
Clinochlore
Cordierite
Cristobalite
Diopside
Enstatite
Faujasite
Fayalite
Fe gehlenite
Feldspars
Ferrosillite
Forsterite
Garnet (andradite, pyrope, grossular)
Gehlenite
Gismondite
Hatrurite
Hedenbergite
Illite
Kalsilite
K aluminosilicates
Kaolinite
KCa aluminosilicate
KCa silicates
K feldspars
KMg silicate
K silicates
Larnite
Leucite
Makatite
Melilite (akermanitegehlenite)
Merwinite
Metakaolinite
Mg silicate
Microcline
Monticellite
Mullite
Muscovite
NaCa silicate
Na melilite
Na silicate (water glass)
Na tremolite
Orthoclase
Paranatrolite
Plagioclases
Quartz
Rankinite
Riebeckite
Sanidine
Sepiolite
Serandite
Silica
Suolunite
Talc
Chemical formula
Reference used
Ca3(SiO3OH)22H2O or
Ca3(Si2O4)(OH)6
Ca2MgSi2O7
NaAlSi3O8
SiO2
CaAl2Si2O8
(Ca, Na)(Mg, Fe, Al, Ti)(Si, Al)2O6
Ca7Mg(SiO4)4
[24a]
Ca2SiO3Cl2
Ca(Fe,Mg)Si2O6
CaO.SiO2.H2O
CaSiO4, CaSi2O5, Ca4Si2O8,
Ca8Si5O18, others
CdSiO3
(MgFe)5Al2Si3O10(OH)8
(MgFe)5Al(Si3Al)O10(OH)8
(MgFe)2Al3(Si5AlO18)
SiO2
CaMgSi2O6 or CaMg(SiO3)2
MgSiO3
Na2Al2Si3.3O10.67H2O
Fe2SiO4
Ca2FeAlSiO7
NaAlSi3O8CaAl2Si2O8, KAlSi3O8
FeSi2O6
Mg2SiO4
Ca3Fe2Si3O12, Mg3Al2Si3O12,
Ca3Al2Si3O12
Ca2Al2SiO7
Ca2Al4Si4O169H2O
Ca3SiO5
CaFeSi2O6 or Ca(FeMg)(SiO3)2
(KH2O)Al2(AlSi)Si3O10(OH)2
KAlSiO4
Al2Si2O5(OH)4
K2CaSiO4, K4CaSi3O9, others
KAlSi3O8
K2MgSi3O8
K2Si4O9, others
Ca2SiO4
KAlSi2O6
Na2Si4O8(OH)24(H2O)
Ca2MgSi2O7Ca2Al2SiO7
Ca3Mg(SiO4)2
Al2Si2O5
KAlSi3O8
CaMgSiO4
Al6Si2O13
KAl2AlSi3O10(OH,F)2
Na2CaSiO4
NaCaAlSi2O7
Na2Si3O7 or Na2SiO3
(Ca,Na)23Mg5Si8O22 (OH)2
KAlSi3O8
Na2Al2Si3O103H2O
NaAlSi3O8CaAl2Si2O8
SiO2
Ca3Si2O7
Na2Fe3Fe2Si8O22(OH)2
KAlSi3O8 or (K, Na)(Si, Al)4O8
Mg4Si6O15(OH)26H2O
Na(MnCa)2Si3O8(OH)
SiO2
Ca2Si2O5(OH)2(H2O)
Mg3Si4O10(OH)2
[2434b]
[18,33,35c47]
[18,30,4853]
[34b,37d,38,47,54,55]
[30,56]
[33]
[35,47,57,58]
[59]
[18]
[25]
[24a,39,60,61]
[25,26,57,6265]
[66,67]
[27b]
[36,68]
[45]
[27b]
[13,18,25,27b,31,33,38,46,47,49,53,56,6973, present study]
[25,30,33,46,74]
[75]
[38d]
[47,74]
[26]
[24,33,45,75]
[74]
[34b,74]
[26,28,30,53]
[24,27b,34b,38,43,47,65,76]
[65a,77]
[78,79]
[36,45]
[27b,55]
[26,29,33,65,78,80]
[58,81]
[27b,40,82]
[83]
[13,25,64,65,74,78,8386]
[24,25,27b,33,38,46,57,61,64,65,87,88, present study]
[89]
[26,84,85,9092]
[13,24,25,27b,30,31,33,34b,53,59,60,62,7880,89,111]
[18,30,33,46]
[38d]
[26,28,30,53]
[24,25,29,33,46]
[55]
[57]
[13,39,45]
[29,30]
[27b,47,82,93, present study]
[27b,37,41,42]
[89]
[26]
[59]
[86]
[26,74]
[38d]
[24,25,27b,35c,e,55,57,61,65, present study]
[13,14,18,24,25,27b,30,31,3336b,c,e,3847,5557,59,61,62,64,65,68,71,72,74
78,80,82,8487,94c99,111, present study]
[2527b]
[60]
[43]
[27b]
[60]
[26,28,29,35,37,44,59,60,63,74,79,90,100]
[77]
[27b,45]
45

Table 3 (continued)
Phase, mineral
Chemical formula
Reference used
Tridymite
Vermiculite
Wollastonite
Zeolites
SiO2
(MgFeAl)3(SiAl)4O10(OH)24H2O
a-Ca3Si3O9 or a-CaSiO3
(Ca, Sr, Ba, Na2, K2)Al2Si210O8
2428H2O
[13,33,47,49,53, present study]

[27b]
[25,27b,30,31,33,38,63,79,89,101,111]
[27b,38d]
Zn-bearing silicates
1.2. Oxides and hydroxides
Alumina
CaAl oxides
CaFe oxide
CaMn oxides
Cd-bearing oxides
Corundum
Cr-bearing oxides
CrFe oxide
Fe oxide
Gibbsite
Goethite
Hematite
Hydrocalumite
KAl oxides
KFe oxide
K hydroxide
K oxide
Lime
Macedonite
Maghemite
Magnetite
MgCrFe oxide
MgFeAl oxide
MgMn oxide
Monteponite
Na hydroxide
Na oxide
Pd oxide
Periclase
Plattnerite
Portlandite
Rutile
Srebrodolskite
Wustite
Zincite
ZnAl oxide
Zn ferrite
ZnTi oxide
[65]
c-Al2O3
Ca3Al2O3, Ca3Al2O6
CaXFeYOZ
Ca2MnO4, Ca4Mn3O10
Al2O3
(Cr, Fe)2O3
Al(OH)3
a-FeOOH
a-Fe2O3
Ca2Al(OH)6[Cl1x(OH)x]3(H2O) or
Ca4Al2Cl2O610H2O
K2Al2O4 or K2Al19O29.5
K3FeO2
KOH
K2O
CaO
PbTiO3
c-Fe2O3
FeFe2O4
Mg(Cr, Fe)2O4
MgFeAlO4
Mg6MnO8
CdO
NaOH
Na2O
PdO
MgO
PbO2
Ca(OH)2
TiO2
Ca2Fe2O5
FeO
ZnO
(Zn, Fe)Fe2O4
ZnXTiYO4
1.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates

Amorphous K, Na, Ca and Mg sulphates
Anhydrite
CaSO4
Aphthitalite
Arcanite
(KNa)3Na(SO4)2
K2SO4
Bassanite
CaK sulphates
Ca langbeinite
CaMg sulphate
Ca sulphate
Cd sulphate
Ettringite
Glaserite
Gypsum
Kieserite (dehydrated)
K sulphide
Langbeinite
Mg thiosulphate
Millosevichite
Na thiosulphate
Oldhamite
Picromerite
Sulphides
CaSO40.5H2O
K2Ca2(SO4)3 or K2CaMg(SO4)3
CaMg3(SO4)4
Ca6Al2(SO4)3(OH)1226H2O
K3Na(SO4)2
CaSO42H2O
MgSO4
K2S
K2Mg2(SO4)3
MgS2O3
Al2(SO4)3
Na2S2O3
CaS
K2Mg(SO4)26H2O
Compounds with sulphide anion
(S2)
[63,82]
[24,38,61,75]
[102]
[89]
[67,103]
[27b,39,86,99]
[103]
[102]
[13,58]
[57]
[27b,45,102]
[13,24,25,27b,33,34b,3642d,4446,55,75,82,86,96,98,99,103,104]
[34b]
[64,65a]
[80]
[105]
[26,105]
[24,25,27b,33,35,37,41,42,45,46,55,57,58,60
63,65,79,89,90,92,96,98,101,104,106,107]
[73]
[33,44]
[27b,34b]
[102]
[75]
[89]
[67]
[105]
[105]
[108]
[13,24,25,27b,30,32,33,3537,3942,45,46,53,55,57,62,79,80,89,96,98,99,101,102,
present study]
[102]
[24a,27b,34b,37,38,42,46,57a,58,6062a,65,75,77,79,89,96,98,106, present study]
[24,26,27b,3638d,45]
[39]
[109]
[31,66]
[65]
[102]
[102]
[74]
[24,27b,3639,4147,55,61,64,65,74,75,77,87,94c,96,98,99,104,106,110,112,113,
present study]
[33,41,42,62,98]
[13,24,25,33,35c,37,38,42,45,46,57
59,62,65,74,77,79,80,84,85,87,89,94c,98,101,103,104,110118, present study]
[44a,65a]
[58,92]
[25,74,79,89,104,118]
[94]
[58,92]
[66]
[24a,57a,61a,65a]
[24,31,37,46,79]
[24a,57a,61a,65a, present study]
[37]
[112f]
[86]
[94]
[13]
[94]
[35,77,112f,119]
Present study
[109,120]
(continued on next page)
46
Table 3 (continued)
Phase, mineral
Chemical formula
Reference used
Sulphites
Compounds with sulphite anion
[120]
Syngenite
Syngenite (dehydrated)
Thenardite
Xanthoconite
SO2
3
K2Ca(SO4)2H2O
K2Ca(SO4)3
Na2SO4
Ag3AsS3
[24a,57a,77]
[25]
[37,117]
[100]
1.4. Phosphates
Al phosphates
Apatite
Apatite (Ca decient)
Berlinite
CaFe phosphate (similar to whitlockite)
CaK phosphate
CaMgK phosphate
Ca phosphates
Chloroapatite
Durapatite
Fe phosphates
Hydroxylapatite
KCa phosphate
K hydrophosphate
K phosphates
K pyrophosphate hydrate
MgCa phosphate
Mg phosphates
Mg pyrophosphate
NaK phosphate
Na phosphates
Whitlockite
Zn phosphate
Ca(PO4)3(Cl, F, OH, CO3) or

Ca5(PO4)3(Cl, F, OH, CO3)
Ca10x(HPO4)x(PO4)6x(OH)2x
AlPO4
Ca9FeH(PO4)7
CaKPO4
Ca9MgK(PO4)7
Ca3(PO4)2, Ca3P2O8, others
Ca(PO4)3(Cl) or Ca5(PO4)3(Cl)
Ca5HO13P3
FePO4, Fe7(PO4)6
Ca(PO4)3(OH), Ca5(PO4)3(OH) or
Ca10(PO4)6(OH)2
KCa(PO4)
KH2PO4
K3PO4, K5P3O10, others
K4P2O73H2O
MgCaPO4
Mg2P2O7
Na6P2O8, others
Ca9Fe(PO4)7 or Ca3(PO4)2
1.5. Carbonates and bicarbonates

Ankerite
Arterite
Baylissite
Butschliite (dimorphous with fairchildite)
CaK carbonate
Calcite
Ca(MgFe)(CO3)2
Mg2CO3(OH)23H2O
K2Mg(CO3)24H2O
K2Ca(CO3)2
Ca2K2(CO3)3
CaCO3
Cr-bearing carbonates
Dolomite
Eitelite
Fairchildite
Hydrocalcite
Hydrotalcite
Kalicinite
K carbonate (potash)
Magnesite
Natrite
Natrofairchildite
Nesquehonite
Nyerereite
Paraalumohydrokalcit
Siderite
CaMg(CO3)2
Na2Mg(CO3)2
K2Ca(CO3)2
CaCO3H2O
Mg6Al2CO3(OH)164H2O
KHCO3
K2CO3
MgCO3
Na2CO3
Na2Ca(CO3)2
MgCO33H2O
(Na0.82K0.18)2Ca(CO3)2
CaAl2(CO3)2(OH)46H2O
FeCO3
1.6. Chlorides, chlorites and chlorates

Ca chloride
Ca chlorite hydrate
Ca hydroxylchloride
CaK chlorides
Cd chloride
Cotunnite
Fe chloride
Halite
K halite
K perchlorate
Sylvite
CaCl2
Ca(ClO)23H2O
CaOHCl
Chlorocalcite type (KCaCl3)
CdCl2
PbCl2
[38d,121]
[27b,33,44,48,56,57,74, present study]
[44,56]
[75,104]
[44]
[101]
[38d]
[26,32,37,44,53,54,56,57,84,92,104,113]
[56]
[104]
[38a,44]
[24,33,37,41,42,4446,56,57,62,79,98,101,122,65]
[79,94]
[94]
[32,59,92,101,123]
[94]
[94c]
[92]
[94]
[44]
[13,26,92]
[33,38d,44,75d, present study]
[44]
[40]
[37]
[37]
[13,111]
[33,46,58]
[13,24,25,27b,30,3338b,4047,53,55
62,64,65,68,71,75,76,79,80,87,89,90,92,94c,98,105108,111,112,118,124, present
study]
[103]
[36,42,45,80,94,98,108, present study]
[37]
[24,25,33,35,37,45,46,62,79,80,89,94, present study]
[24a,57a]
[60]
[37, present study]
[13,33,37,5759,89,105,112,113,117,124,125]
[103,124]
[105,117,124, present study]
[94, present study]
[94]
[37]
[24a]
[40,45]
Zn chloride
ZnCl2
[38]
[60]
[38]
[92]
[67]
[126]
[127d]
[24,37,38,56,68,94c,99,113,117,126, present study]
[24,75]
[68c]
[13,24,25,30,31,33,3538,4547,53,5659,62,64,65,77,79,80,84
87,92,94c,96,99,100,103,111118,125, present study]
[126,128]
1.7. Nitrates
Nitrates
Nitre (niter)
KNO3
[94c]
[35c,68c]
NaCl
K0.2Na0.8Cl or K0.4Na0.6Cl
KClO4
KCl
47
Table 3 (continued)
Phase, mineral
Chemical formula
Reference used
1.8. Glass
Various elements
[13,2427b,2931,3335b,4648,5557,65,69,71,74,76,88,97,101,110,116,129
131, present study]
1.9. Other inorganic phases

Amorphous (non-glass) inorganic material
Elemental Al
Elemental Pb
K-Mo selenide
Margaritasite
Metallic alloys and pure metals
Al
Pb
K2Mo3Se18
(CsKH3O)2(UO2)2V2O8H2O
Various elements
2. Organic matter
2.1. Organic phases
Char (unburned organic matter, semi-coke,
coke, soot, tar, others)
Chlorobenzene
Chlorophenol
Cyanides
Na cyanate
Polychlorinated dioxins
Polychlorinated furans
Polycyclic aromatic hydrocarbons
2.2. Organic minerals
Weddelite (Ca oxalate dihydrate)
Whewellite (Ca oxalate dehydrate)
Whewellite (Ca oxalate monohydrate)
C6H5Cl
C6H5ClO
Salts of CNNaOCN
Chlorinated hydrocarbons
Halogenated organic compounds
Polyaromatic or polynuclear
hydrocarbons
Ca(CO2)2(H2O)2 or CaC2O42H2O
CaC2O4
CaC2O4H2O
3. Fluid matter
[24,35c,48,53,65,86,94,111, present study]

[27b,38b]
[109]
[100]
[73]
[27b,108]
[13,14,18,24,27b,31,35,40,55,58,60,63,73,76,84,86,95,97,106,114,126,129,130,132
136, present study]
[132]
[132]
[137]
[128]
[10,14,95,121,126,132,138,139]
[10,14,95,126,132,138140]
[14,132,137,141]
[94c]
[94c]
[35c]
[28,53,102]
Hydrated or leached ash.

Municipal solid waste ash.
Low-temperature ash produced in oxygen plasma (100250 C).
d
Sewage sludge ash.
e
From soil.
f
In char.
b
c
(2) The long term experience and knowledge achieved for the
phase composition of the most studied ashes, namely from
coal, peat, petroleum coke and municipal solid waste or
refuse-derived fuel ([27,142146] and references therein)
have not been implemented very successfully in the eld
of BA. Therefore, the use of unsuitable scientic approaches,
models and procedures, incomplete data or unusual and
sometimes inappropriate terms and interpretaions is common in many investigations of BA (see below).
(3) A serious omission is the limited description of the specic
type, place and manner of BA collection, as well as storage
and processing conditions. This is a serious problem for the
reliable identication and characterization of phases in BA.
Representative sampling problems associated with BA also
occur and some of them have been discussed [14,95,147].
(4) The phases in BA are a result of combustion of biomass originating from natural and anthropogenic formation processes
and a signicant fraction in BA can contain other non-biomass phases ([1,2,27,144] and references therein). Therefore,
BA produced from contaminated biomass (semi-biomass)
should always be considered separately from BA generated
from natural biomass due to the different origin, composition and potential use.
(5) The lack of generally accepted terminology, classication
systems and standards worldwide for the phase composition
of BA leads to very serious misunderstanding during the
investigations. The biggest problem seems to be the absence
of appropriate phase classications for BA in contrast to
some other ashes. For example, there are systematic and relatively strict phase specications for coal ash (which can
also be applied to BA) including: (1) inorganic matter (crystalline and non-crystalline) such as mineral classes, groups
and species and amorphous phases and (2) organic matter,
namely chars produced from different lithotypes, microlith-
(6)
(7)
(8)
(9)
(10)
otype groups and macerals; and which are well recognized

worldwide and relatively well characterized ([142,143,148]
and references therein).
Detailed and complete data sets from simultaneous chemical and phasemineral analyses for various BAs are scarce.
Thus, limited systematic interpretations can be made from
investigations [89,131,149].
Most studies used the data from ash yield or the bulk chemical composition of ash to explain mineral matter, mineral
composition, inorganic matter or inorganics in biomass
and BA, which is not fully correct and can lead to confusion
in many cases (see below and [1,2]).
The common scientic approach used is to study the concentration and behaviour of individual elements (Ca, Cl, K, Na, P,
S, Si and trace elements) for explaining and evaluating different technological and environmental problems related
to BA. However, the actual reasons for such problems in a
multicomponent system like that for BA are most likely connected with modes of element occurrences, namely specic
phases and minerals that contain such elements, similar to
coal ash (see Part 2 and [143,150,151] and references
therein).
The methods for phase and mineral investigations of BA
have not been developed and implemented very well.
Extraction procedures are dominantly used for the identication and quantication of the inorganic and organic phase
composition of BA. Unfortunately, the direct methods for
determination of phases in BA are not common (see below).
Some analytical concerns associated with BA have been discussed ([14,95,147] and references therein).
Sequential chemical fractionation is mostly used to distinguish the speciation (modes of occurrence or chemical forms
of combination) of elements in BAs. However, this indirect
procedure cannot be applied to identify the actual modes
48
(11)
(12)
(13)
(14)
(15)
(16)
of occurrence of elements in a multicomponent system.

Leaching alone has many limitations and can be used only
to provide preliminary information for some possible associations of elements in phases (see below). Other direct methods commonly applied for coal and coal products ([145,146]
and references therein) provide better information and they
should always be used additionally for such a purpose.
Many ndings about the behaviour of organic and inorganic
matter during biomass heating are based only on theoretical
equilibrium and stoichiometric calculations of chemical
data. These indirect investigations may be quite unrealistic
for actual predictions of phases in a multicomponent system
under non-equilibrium conditions (see for example [46]).
Such calculations can be used only to provide a subsidiary
or preliminary prediction procedure of the real and direct
(input, output) phase studies of the systems.
The variable ash-melting points of biomass fuels have been
discussed in numerous studies. However, it should be stated
that melting points occur only for pure (monocomponent)
systems, while biomass ash (similar to coal ash) is a multicomponent system of powder material and cannot have a
specic melting point (see for example [152]). Therefore,
BA has three or four characteristic and measurable ashfusion temperatures because ash melting occurs over a wide
temperature range (see below).
The challenges and advantages related to BA utilization are
only at an initial stage of investigation and they need further
clarication by extensive and detailed studies (see Part 2).
There is a strange acceptance that BA does not contain toxic
metals like in the case of coal ash [13,153]. However, certain
results for BAs [41,95,108,127,154158] concerning the concentrations of elements such as Ag, As, Ba, Cd, Cl, Cr, Cu, Hg,
Mn, Mo, Ni, Pb, S, Sb, Se, Sn, Th, Tl, U, V and Zn are very disturbing (see below and Part 2). Systematic studies about
trace elements in biomass and BA are only at an initial stage
of investigation and more work is needed.
Washing to remove water-soluble phases prior to use of BAs
may reduce some technological and environmental problems.
However, such future large-scale leaching may create new
environmental concerns related to the fate of mobile phases
containing alkali metals, Cl, S, P and some hazardous trace
elements associated with these phases (see below and Part 2).
Regulations exist in some countries which specify the limiting and guiding values for the contents of some elements
(Ca, Cd, Cl, Co, Cr, Cu, K, N, Ni, Pb, S, V, Zn) in biomass fuels
and their BAs in respect of their unrestricted use. However,
the bulk concentrations of these elements are less informative than the abundance and behaviour of the forms in
which they are present (see below and Part 2).
The above listed problems show that additional, systematic and

detailed chemical and phasemineral studies of BA based on
proved, improved or new approaches are required to reduce uncertainties. There are thus ample opportunities for new research in
this area. Here, based on a critical review of publications and some
own investigations an attempt will be undertaken to:
(1) Compile and systematize a reliable database related to the
composition of BAs.
(2) Describe the basic ndings and clarify some of the problems
associated with the composition of these combustion
residues.
(3) Supply additional results related to composition and properties of BAs.
(4) Indicate the potential applications and environmental risks
connected with BAs.
(5) Understand how the fundamental knowledge on the composition and properties may be exploited for the most innovative and sustainable utilization of these combustion
residues.
The present overview includes the composition and application
of BA and it was split in two parts for better systematisation and
presentation. Part 1 comprises the phasemineral and chemical
composition and classication of BAs, while Part 2 incorporates potential utilization, technological and ecological advantages and
challenges related to BAs.
2. Materials, methods and data used
The results in this overview are obtained from: (1) reference
peer-reviewed investigations and (2) reference peer-reviewed data
including our own new data and studies with novel interpretation
from both previous overviews [1,2] plus additional own data in the
present overview. For better differentiation, they are referred to as:
(1) reference investigations and (2) present study throughout
the text, respectively.
The phases and minerals identied or assumed (with uncertain
identication) in BAs are given in Table 3 using mostly peer-reviewed investigations [10,13,14,18,24141] plus own data. Eight
biomass samples were collected and studied for additional clarication of the phase composition of BAs in the present work (Table 4). They include beech wood chips (BC), corn cobs (CC),
marine macroalgae (MM), weathered plum pits (PP), rice husks
(RH), switchgrass (SG), sunower shells (SS) and walnut shells
(WS). The majority of investigations up to now have been concentrated dominantly on woody biomass and wheat straw as solid biofuels. Most of these eight samples are herbaceous and agricultural
residues and algae (sea lettuces) and much less is known about
them. The selection of these samples is also based on their highly
variable: (1) structural composition and especially (2) inorganic
chemical composition (Table 4 and Fig. 1) according to the reference data [1,2,159,160]. Another big advantage of these samples
for comparative investigations is that they belong to all four inorganic chemical types of biomass (S, C, K, and CK types) and
different sub-types (Fig. 1) that have been specied recently [1].
Additionally, ve samples from them belong to the low acid K
and CK types and sub-types, which are among the most problematic biomass resources from technological and environmental
points of view [2]. The samples collected were between 2 and
5 kg in weight and they were air dried under ambient conditions
during a period of over 12 months. After that, visible contaminants
such as sand, soil or shell particles were eliminated manually from
RH and MM. Then the samples were cut/crushed (CC, PP, WS) and
ground (BC, CC, MM, PP, RH, SS, SG, WS) to a particle size of
<500 lm (BC, MM, RH, SG, SS) or <1000 lm (CC, PP, WS). Finally,
they were investigated using light microscopy, powder X-ray diffraction (XRD), differential-thermal (DTA), thermo-gravimetric
(TGA) and chemical analyses, as well as some leaching, precipitation, ashing and other procedures.
An ordinary stereomicroscope under transmitted and reected
light was used for optical observations. XRD patterns of nely
ground samples were recorded by D2 Phaser Bruker AXS and DRON
3 M diffractometers, and collected at 1070 2h using Cu and Co Ka
radiations, respectively. The high-temperature ashes (HTAs) of biomass samples were produced in an electric oven (Carbolite) with
static air at 500 10 C for 2 h with a heating and cooling rate of
about 5 C min1. The above temperature and holding time were
selected as the lowest ones for gentle and successful incineration
of biomass prior to intensive decomposition (above 500 C) of carbonates and some sulphates which are typical minerals for biomass and BA.
49

Table 4
Data for eight biomass samples (air-dried basis) additionally studied, wt.% (indicated otherwise).
Characteristic
Sunower
shells
SS
Walnut
shells
WS
Billa Soa,
Bulgaria
08.2008
Debnevo,
Bulgaria
08.2008
<0.5
451
Mead, Nebraska,
USA
2003
Two mixed
harvests
(50:50 vol.%)
<0.5
263
<0.5
250
<1
833
1000
476
286
275
883
6.75
5.57
6.66
5.20
5.12
5.28
1.60
19.81
0.67
2.12
1.63
3.47
0.88
1.4
1.31
0.94
0.86
0.84
0.80
0.8
2.14
1.70
1.47
1.44
15.1
28.24
23.58
20.50
17.17
11.69
0.3
0.66
0.52
0.51
0.50
0.47
7.8
5.14
4.23
4.17
4.14
2.9
2.97
2.36
1.95
1.86
1.67
0.9
0.90
0.77
0.57
0.52
0.51
61300
170
61100
200
61300
430
61300
130
1.5
18.50
17.48
17.41
17.37
17.37
17.22
>1500
270
61100
80
61300
120
61300
150
Reference data
VM (db)
FC (db)
A (db)
Sum
C (daf)
O (daf)
H (daf)
N (daf)
S (daf)
Cl (daf)
Sum
Cel (daf)
Hem (daf)
Lig (daf)
Sum
Ext (daf)
82.0
17.2
0.8
100.0
47.2
46.6
6.1
0.1
0.01
0.01
100.02
45.2
32.7
22.1
100.0
1.1
81.2
16.8
2.0
100.0
47.8
45.6
5.9
0.5
0.01
0.23
100.04
48.1
37.2
14.7
100.0
7.0
50.5
25.9
23.6
100.0
41.7
44.3
6.0
2.1
2.51
3.34
99.95
28.5
65.5
6.0
100.0
15.1
80.8
17.8
1.4
100.0
49.9
42.4
6.7
0.9
0.08
0.01
99.99
23.7
22.0
54.3
100.0
5.4
62.8
19.2
18.0
100.0
49.3
43.6
6.1
0.8
0.08
0.12
100.00
43.8
31.6
24.6
100.0
6.6
80.4
14.5
5.1
100.0
49.6
43.4
6.1
0.7
0.11
0.08
99.99
48.7
38.4
12.9
100.0
8.0
76.0
20.9
3.1
100.0
50.4
42.9
5.5
1.1
0.03
0.10
100.03
56.5
28.0
15.5
100.0
2.6
59.3
37.9
2.8
100.0
49.8
42.4
6.2
1.4
0.09
0.15
100.04
28.1
26.6
45.3
100.0
2.7
HTA (550600 C)
SiO2
CaO
K2O
P2O5
Al2O3
MgO
Fe2O3
SO3
Na2O
TiO2
Cl2O
MnO
Sum
DAI
Ref.
12.33
67.80
2.59
2.29
0.12
11.43
1.09
0.80
0.89
0.10
0.16
0.40
100.00
0.2
[1,2]
27.65
13.19
35.49
6.96
2.49
2.05
1.55
7.14
1.26
0.13
2.01
0.08
100.00
0.5
[1,2]
1.44
10.79
13.37
8.50
0.74
10.89
1.63
22.42
17.32
0.01
12.86
0.03
100.00
0.3
[1,2,159,160]
3.59
14.65
44.88
20.12
0.11
11.62
0.68
2.47
0.46
0.02
1.35
0.05
100.00
0.1
[1,2]
94.38
0.97
2.29
0.54
0.21
0.19
0.22
0.92
0.16
0.02
0.08
0.02
100.00
19.0
[1,2]
66.09
10.19
9.62
3.91
2.21
4.70
1.36
0.83
0.58
0.28
0.16
0.07
100.00
2.4
[1,2]
23.46
15.18
28.29
7.07
8.67
7.27
4.23
4.03
0.79
0.15
0.85
0.01
100.00
0.6
[1,2]
23.29
16.70
32.99
6.20
2.40
13.49
1.50
2.20
1.00
0.10
0.12
0.01
100.00
0.4
[1,2]
Code
Source
Collection time
Note
Size reduction (mm)

Bulk density (loose)
(kg m3)
Bulk density (shaken)
(kg m3)
pH of leachate (solid
liquid = 1:10 mass
ratio)
Electrical conductivity
of leachate (mS/cm)
DWR
Ash (500 C/2 h)
Ash (700 C/1 h)
Ash (900 C/1 h)
Ash (1100 C/1 h)
Ash (1300 C/1 h)
Ash (1500 C/1 h)
Fluid AFT
Ash (500 C/2 h) bulk
density (loose)
(kg m3)
Beech wood
chips
BC
Corn cobs
Marine macroalgae
Plum pits
Rice husks
Switchgrass
CC
MM
JRS Rosenberg,
Germany
01.2009
Produced size
is 14 mm
Debnevo,
Bulgaria
08.2008
Tsarevo, Bulgaria
PP
RH
SG
Kovachevo, Bulgaria
08.2009
Cleaned from sand
and shell grains
Debnevo,
Bulgaria
08.2008
Weathered
for 1 year
08.2007
Cleaned from sand
and soil grains
<0.5
454
<1
412
<0.5
954
<1
889
479
435
1250
5.15
5.32
0.70
Abbreviations: A, ash yield; AFT, ash-fusion temperature; Cel, cellulose; daf, dry ash-free basis; DAI, detrital/authigenic index (Si + Al + Fe + Na + Ti oxides/
Ca + Mg + Mn + K + P + S + Cl oxides); db, dry basis; DWR, dry water-soluble residue; Ext, extractives; FC, xed carbon; Hem, hemicellulose; HTA, high-temperature ash; Lig,
lignin; VM, volatile matter.
The thermal experiments include a gradual heating of HTAs

produced at 500 C/2 h via 200 5 C intervals in the electric oven
under atmosphere of static air. The heating was conducted at 700,
900, 1100, 1300 and 1500 C or up to the uid ash-fusion temperatures of the samples (excluding only RH), namely 1100 C (CC,
SG), 1300 C (BC, MM, PP, SS, WS) and 1500 C (RH). The sample
RH has a uid ash-fusion temperature higher than 1500 C. Initial

portions of HTA samples (0.10.9 g) spread out in a layer (about
13 mm thickness) at the bottom of ceramic crucibles (5 3 cm
in diameter and 3.5 cm height) were heated up to the respective
temperature for each experiment. The heating and cooling rate
was about 10 C min1. A holding time at the xed temperature
50
Fig. 1. Positions of eight biomass varieties in some classication systems based on data from: (a) proximate; (b) ultimate; (c) structural; and (d) ash analyses [2], wt.%.
Abbreviations: B, bituminous coal; BC, beech wood chips; CC, corn cobs; daf, dry, ash-free basis; db, dry basis; FC, xed carbon; L, lignite; MM, marine macroalgae; P, peat; PP,
plum pits; RH, rice husks; S, sub-bituminous coal; SG, switchgrass; SS, sunower shells; VM, volatile matter; WS, walnut shells.
was 1 h and then gradual cooling to ambient temperature was carried out. This holding time is based on the former investigations
[25,161164] that found a time interval of P30 min to be entirely
sufcient to achieve equilibrium in the system. Breaking of the
ceramic crucibles and gentle handpicking under a binocular microscope were applied to separate the fused material (slag) that was
formed at the maximum temperatures. Despite that, a few and ne
ceramic particles from the crucibles were observed microscopically
to occur as contaminants in BC, MM, PP and SS slags. These contaminants were identied as mullite, plagioclase and quartz by
XRD for these four samples heated at 1300 C. Additionally, DTA
and TGA analyses were conducted using a Stanton Redcroft STA
760 apparatus. These experiments were carried out for 1020 mg
of biomass samples and their HTAs produced at 500 C/2 h. The
samples were gradually heated in corundum crucibles from ambient temperature to 1400 C under oxidising conditions as the ow
rate of air was 30 ml min1 and the heating rate was 10 C min1.
The thermally treated HTAs are dened below as ashes and slags.
Dry, water-soluble residues (DWRs) were isolated from the biomass samples by evaporation and precipitation of the water-soluble solutions leached. The leachates from this extraction procedure
were generated from 10 g of biomass samples placed in glass containers with 100 ml of distilled water and soaked for 24 h at ambient temperature. The suspensions were periodically stirred and
nally decanted and ltered. The pH and electrical conductivity
values were measured in the generated water solutions by a bench
pH-mV-conductivity meter PC 5000L (VWR International Ltd.).
Then the leachates were placed in a drying oven at 80 C for evaporation and crystallization giving DWRs. These leaching and precipitation procedures are similar to those applied for coals
[165,166] and refuse-derived fuels [27].
The contents of trace elements (Ag, Au, B, Be, Cd, Cr, Cu, Mn, Ni, Rb,
Se, Zn) in biomass ashes (500 C/2 h) were determined by inductively coupled plasma - mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS), respectively, following: (1) acid digestion
of the samples by HCl, HNO3 and HF and subsequent measurement
of the solutions (for B and Mn) by Perkin Elmer ELAN DRC-e mass
spectrometer and (2) preparation of discs after fusion of the samples
with Li2B4O7 at 1000 C and subsequent measurement of the glass
discs (for other elements) by the above apparatus combined with
New Wave UP193FX excimer laser ablation system. NIST SRM
glasses 610 and 612 were used as external calibration standards.
3. Results and discussion

3.1. Common observations about biomass ash
3.1.1. Denition, specication and terminology clarication
An initial clarication of certain terminology, denitions and
specications is useful due to some misunderstandings and unclear interpretations in the literature about the terms used during
characterization of biomass ashes. The proposed description below
related to the composition, content and origin of phases and minerals in BA is based on detailed investigations of other solid fuel
ashes, particularly coal ashes [27,148,150,163,164,166168], as
well as some data for biomass and BA (Table 3 and [1,2]).
Biomass ash is the solid residue that results from the combustion of biomass. This combustion residue is a complex inorganic
organic mixture with polycomponent, heterogeneous and variable
composition and contains intimately associated solid, liquid and
gaseous phases (Table 1) with different origin (Table 2).
BAs can be laboratory and industrially generated combustion
products. The laboratory-produced BAs include:
(1) Low-temperature ash (LTA) prepared in oxygen plasma at
100250 C;
(2) High-temperature ash (HTA) produced in air normally above
500 C; and
(3) Slag generated from completely molten ash; at regulated
temperatures.
On the other hand, the industrial BAs consist of.
(1) Bottom ash (from dry-ash discharge boilers) or slag (from
melt discharge boilers).
(2) Fly ash (from ue gas discharge systems); produced in
industrial combustion and gasication installations at temperatures commonly between 800 and 1600 C.
The chemical composition of BA comprises: (1) major (>1%); (2)
minor (10.1%); and (3) trace (<0.1%) elements; according to their
elemental concentrations, where the major and minor elements
are mostly expressed as oxides (see Section 3.1.2).
The phasemineral composition of BA includes:
(1) Mostly inorganic matter composed of non-crystalline (amorphous) and crystalline to semi-crystalline (mineral)
constituents.
(2) Subordinately organic matter consisting of char and organic
minerals.
(3) Some uid matter comprising moisture and gas and gas
liquid inclusions associated with both inorganic and organic
matter (Table 1 and Sections 3.2 and 3.3).
The phases and minerals in BA can be divided into: (1) forming
(>10%); (2) major (110%); (3) minor (0.11%); and (4) accessory
(<0.1%); based on their contents (see Section 3.2).
BA is composed of original (primary) or newly formed (secondary and tertiary) inorganic and organic solid phases generated from
natural (authigenic and detrital) and technogenic inorganic, organic and uid matter during biomass combustion. Therefore, the
phases and minerals in BA can be classied in origin as:
(1) Primary, namely pre-existing or original minerals and
phases in biomass that have undergone no phase transformations during combustion.
(2) Secondary such as new phases formed during combustion
process.
51
(3) Tertiary, namely new minerals or phases formed during

transport and storage of BA (Table 2 and Sections 3.2 and
3.3).
Ash is one of the most studied characteristics of biomass, but
unfortunately still with relatively poor understanding. The reason
for this problem is the complex character of this term. Therefore,
the differentiations and specications of terms such as ash yield
or ash content (A), ash, inorganic matter and mineral matter related to biomass (they are also valid to BA) are a necessity. It
should be stated that these terms are not synonymous because
they comprise constituents with different composition, quantity
and origin, similar to coal [1,2,145,146,169,170].
BA is the solid residue that results from the complete or incomplete combustion (or occasionally low-temperature oxidation) of
the organic matter in biomass. Hence, the term biomass ash comprises the inorganic residue without or with some amount of unburnt organic matter resulting from the combustion of biomass
at laboratory or industrial conditions, as specied above. The ash
yield of biomass or BA is just the measured quantity of the incombustible inorganic residue resulting from the complete combustion
(or oxidation) of biomass or BA at laboratory conditions.
The inorganic matter of biomass or BA comprises inorganic and
solid crystalline, semi-crystalline and amorphous phases (Table 1
and [2]). The actual mineral matter of biomass or BA, as a part of
inorganic matter, excludes inorganic amorphous matter and includes only minerals and mineraloids that belong to mineral classes, groups and species strictly divided, dened and characterized
in the mineralogical sense (Tables 1 and 3 and [2]). Hence, constituents such as organic matter, char and inorganic elements (Al, Ca,
Cl, Fe, K, Mg, Mn, Na, Si, Ti, trace elements) associated with organic
matter, namely:
Covalently and ionically bound in the organic matter (for example, organometallic compounds).
Combined in ion-exchangeable forms and as salts of carboxylic
acids in organic matter.
Present as discrete organic minerals; are not included in the
inorganic matter of biomass or BA [2], which is similar to coal
[145] and coal ash [146].
It should be stated that the ash yield itself brings relatively limited information when the composition, abundance and origin of
the biomass and BA constituents are not considered. Hence, the
ash yield should always be interpreted together with the composition, content and origin of constituents in biomass or BA. Such
interpretations have a great importance for elements and phases
in biomass or BA because their modes of occurrence are related
mostly to both organic and inorganic forms and mixed natural
and technogenic origin. The ash yields can be measured routinely,
while the actual determination of bulk inorganic and mineral contents, as well as the complete isolation of inorganic and mineral
constituents from biomass or BA, are a complex procedure and
cannot be quickly and routinely achieved. Even the LTA yield of
biomass is not the actual inorganic or mineral matter of biomass,
as also observed for coal [145]. Despite the above limitations, the
ash yield is still an important parameter for approximating:
Bulk inorganic matter.
Predominant afnity of elements and compounds to inorganic
or organic matter.
Possible contamination of biomass.
3.1.2. Chemical composition
The composition of BA depends on many factors including:
52
(1) Biomass resource (type of biomass, plant species or part of

plants, growing processes and conditions, age of the plants,
fertilizer and pesticide doses used, harvesting time, collection technique, transport, storage, pollution, processing, others) [1].
(2) Biomass combustion (fuel preparation, combustion technology and conditions, collection and cleaning equipments).
(3) Transport and storage of BA.
The elements in biomass and BA can be classied into major,
minor and trace elements according to their elemental concentrations, as mentioned above. The decreasing order of abundance of
major and minor elements in biomass is variable. For example,
the reference investigations show that the major elements in
angiospermous and gymnospermous plants are C > O > H > N >
Ca > K,
whereas
the
minor
elements
are
normally
S > Mg > P > Cl > Na [159]. Another study reveals that this order is
C > O > H > N > K > Ca for major elements and S > (Cl, Mg, P) > Si
for minor elements in plants [108]. The chemical data from the
present study related to the composition of 86 varieties of biomass
and their groups and sub-groups specied have been reported recently [1]. This study reveals that in decreasing order of abundance, the major elements are commonly C > O > H > N > Ca > K,
the minor elements normally include Si > Mg > Al > S > Fe > P > Cl > Na, and the trace elements are Mn and Ti plus other
elements in biomass. There are many individual cases among biomass varieties, where the above orders for certain elements are
interchanged. The organic-forming elements in biomass are normally C, O, H, N and S, whereas the inorganic-forming elements
are commonly the other elements. However, some proportions
from the organic-forming elements also occur in inorganic matter,
whereas parts of the inorganic-forming elements are also present
in organic matter, as also observed for coal [1].
The reference investigations show that in decreasing order of
abundance the contents of major and minor elements in plant
ashes are commonly Si > (Mg, P) > S > (Ca, K) > Na > Al > (Fe,
Cl) > Mn > Ti [171]. The chemical data from the present study (10
oxides normalized to 100% plus Mn contents) related to the traditional ash analyses of 86 varieties of biomass and their groups and
sub-groups specied have been reported recently [1]. This study
reveals that the major and minor elements in BA, in decreasing
order of abundance, are commonly O > Ca > K > Si > Mg > Al > Fe >
P > Na > S > Mn > Ti plus some Cl, C, H, N and trace elements.
The oxide contents in BAs are normally SiO2 > CaO > K2O > P2O5 > Al2O3 > MgO > Fe2O3 > SO3 > Na2O > MnO > TiO2. BA from natural
biomass is commonly enriched in Mn > K > P > Cl > Ca > Na > Mg
and depleted in Al > Ti > Fe > Si > S in comparison with coal ash.
Similar to biomass, there are many individual cases among BAs,
where the above orders for certain oxides and elements are interchanged. The major and minor elements in BA (or the so called ashforming elements) can be all elements listed above represented as
elemental contents or more commonly as oxides in BA. The data
also demonstrate that the chemical composition of BAs has extremely large variations and this is due to the highly variable contents
of bulk inorganic matter and different genetic classes of inorganic
matter in biomass varieties.
The chemical ash composition of the specied biomass groups
and sub-groups as well as four solid fossil fuel types from the present study are given herein (Table 5). This ash composition for major and minor elements has been reported and described in detail
recently [1]. Additionally, only the contents of 12 trace elements
enriched in eight BAs are provided in Table 6. The specic problems related to the concentrations and modes of occurrence of
trace elements in biomass and BA are beyond the subject of the
present study and they will be characterized in further publications. Here, it is interesting to note that Ag, Au, B, Be, Cd, Cr, Cu,
Mn, Ni, Rb, Se and Zn in some of these BAs can show higher contents than the respective Clarke values (worldwide average contents) for coal ashes (Table 6). This comparison is evaluated by
the enrichment/depletion factor (EDF) dened as a ratio of the element content in BA to the respective Clarke value in coal ash [172].
For example, the decreasing order of trace elements with over
Clarke concentrations based on the mean EDF values for the eight
BAs (Table 6) is: B (23.5) > Au (18.2) > Cd (4.9) > Cr@Mn (3.8) > Ag
(3.5) > Zn (2.6) > Be@Cu@Se (2.5) > Ni (2.0) > Rb (1.8). It can be
seen that the above listed elements belong mostly to chalcophile
and siderophile groups and, to a lesser extent, noble, lithophile
and non-metal groups according to the mineralogical classication
of elements [173]. Despite the limited BAs studied such a preliminary geochemical comparison indicates elements that may have
some environmental impacts and/or industrial potential for BA.
For instance, the data (Table 6) point out that some regulated toxic
and potentially toxic trace elements [174,175] in BA such as Ag, Be,
Cd, Cr, Cu, Mn, Ni, Se and Zn might cause some environmental pollution of the air, water, soil and plants during BA utilization. On the
other hand, the concentrations and modes of occurrence of some
trace elements such as Ag, Au, B, Cr, Mn and others may have a resource recovery potential from certain BAs (see Part 2). Hence, the
enriched and/or hazardous elements in BA should have a more detailed environmental concern and economical assessment.
Finally, the bulk chemical composition of biomass and BA is an
important characteristic; however, it is quite insufcient for a reliable explanation of elemental behaviour during biomass and BA
utilization. The abundance, origin and performance of modes of
element occurrence (minerals and phases) in biomass and BA are
needed to fully understand this elemental behaviour (see Sections
3.2-3.4 and Part 2).
3.1.3. Content and concentration trend
The present study shows that the ash yield (dry basis) determined at 550600 C for 86 varieties biomass is in the interval of
0.146% (mean 6.8%) [1]. It is interesting to note that some seaweeds can even have more than 50% ash content [108]. The ash
yield normally decreases in the order: animal biomass > aquatic
biomass > contaminated biomass > herbaceous and agricultural
biomass > wood and woody biomass [1]. For coal (dry basis), the
ash content (815 C) is in the relatively more narrow range of 6
52% (commonly 630% and mean about 21%) and normally shows
much higher value than in biomass [1].
The reference investigations also reveal that wood and woody
biomass has lower ash content compared with herbaceous and
agricultural biomass [95,126,176,177]. The ash yield in wood and
woody biomass commonly decreases in the order: foliage, leaves
or needles P bark > branches or twigs > wood stems or stumps
[108,178182]. It was also found that:
Temperate-climate woods yield less ash than tropical and subtropical woods [132].
Hard wood has higher ash content than soft wood [5,14,183].
The ash yield of wood is reduced with age [178].
On the other hand, herbaceous and agricultural biomass
(straws, grasses, cereals and fruits) has higher ash content than
wood and woody biomass because the former biomass has different organic structure, rapid metabolism and takes up much more
nutrients during the growing periods [95,126,176,177]. The ash
yields of herbaceous biomass also vary within the parts of the
plant, namely: leaves > reproductive organs > stems [131,177].
The annual species and especially grasses contain high ash contents [184] and the ash yields decrease with increasing lignin
contents in grasses [185]. It was identied that the ash contents
in grasses decline during late summer and then rise again during
53
Table 5
Chemical ash composition of biomass groups and sub-groups (86 varieties of biomass) plus algae and four solid fossil fuel types based on high-temperature ash analyses
(normalized to 100%), wt.%. The Mn contents are additionally given (based on [1]).
Biomass group and sub-group
SiO2
CaO
K2O
P2O5
Al2O3
MgO
Fe2O3
SO3
Na2O
Sum
Mn
Samples
43.03
5.79
83.46
10.75
2.19
31.99
3.48
0.66
13.01
5.09
0.12
15.12
6.07
1.10
14.57
3.44
0.37
9.54
2.78
0.36
11.66
2.85
0.22
29.82
0.29
0.06
1.20
100.00
1.32
0.08
3.57
28
28
28
2. Herbaceous and agricultural biomass (HAB)

Mean
33.39
14.86
Minimum
2.01
0.97
Maximum
94.48
44.32
26.65
2.29
63.90
6.48
0.54
31.06
3.66
0.10
14.60
5.62
0.19
16.21
3.26
0.22
36.27
3.61
0.01
14.74
2.29
0.09
26.20
0.18
0.01
2.02
100.00
0.13
0.02
0.46
44
44
44
2.1. Grasses (HAG)

Mean
Minimum
Maximum
46.18
8.73
84.92
11.23
2.98
44.32
24.59
2.93
53.38
6.62
3.14
20.33
1.39
0.67
2.59
4.02
1.42
8.64
0.98
0.58
1.73
3.66
0.83
9.89
1.25
0.09
6.20
0.08
0.01
0.28
100.00
0.31
10
10
10
2.2. Straws (HAS)

Mean
Minimum
Maximum
43.94
7.87
77.20
14.13
2.46
30.68
24.49
12.59
38.14
4.13
0.98
10.38
2.71
0.10
5.57
4.66
1.67
14.10
1.42
0.41
2.82
3.01
1.18
4.93
1.35
0.16
3.52
0.16
0.02
0.33
100.00
0.09
0.02
0.28
9
9
9
2.3. Other residues (HAR)

Mean
Minimum
Maximum
24.47
2.01
94.48
16.58
0.97
44.13
28.25
2.29
63.90
7.27
0.54
31.06
4.90
0.11
14.60
6.62
0.19
16.21
4.84
0.22
36.27
3.80
0.01
14.74
3.05
0.12
26.20
0.22
0.01
2.02
100.00
0.16
0.02
0.46
25
25
25
3. Animal biomass (AB)

Mean
Minimum
Maximum
2.90
0.02
5.77
49.04
41.22
56.85
7.67
3.16
12.19
28.17
15.40
40.94
1.69
1.01
2.37
2.75
1.38
4.11
0.35
0.25
0.45
3.91
3.59
4.24
3.50
0.60
6.41
0.02
0.01
0.03
100.00
0.05
0.01
0.09
2
2
2
4. Mixture of biomass (MB)

Mean
Minimum
Maximum
44.19
34.75
57.83
17.48
11.51
25.70
6.00
3.11
7.76
5.72
1.08
18.07
10.82
9.77
11.35
3.52
2.31
4.77
6.34
4.19
10.44
2.66
1.88
4.62
2.53
1.25
3.18
0.74
0.52
0.95
100.00
0.16
4
4
4
5. Contaminated biomass (CB)

Mean
Minimum
Maximum
35.73
3.39
60.10
18.30
7.63
26.81
3.45
0.16
9.70
3.64
0.20
15.88
15.41
3.08
53.53
3.60
1.57
6.45
9.78
0.82
22.18
3.45
0.99
10.55
1.90
0.54
4.06
4.74
0.32
27.58
100.00
0.15
0.02
0.23
8
8
8
All varieties of biomass (AVB)

Mean
Minimum
Maximum
29.76
0.02
94.48
25.27
0.97
83.46
17.91
0.16
63.90
5.71
0.20
40.94
5.51
0.10
53.53
5.42
0.19
16.21
4.00
0.22
36.27
3.28
0.01
14.74
2.48
0.09
29.82
0.66
0.01
27.58
100.00
0.75
0.01
3.57
86
86
86
Natural biomass
Mean
Minimum
Maximum
29.14
0.02
94.48
25.99
0.97
83.46
19.40
2.19
63.90
5.92
0.54
40.94
4.49
0.10
15.12
5.60
0.19
16.21
3.41
0.22
36.27
3.27
0.01
14.74
2.54
0.09
29.82
0.24
0.01
2.02
100.00
0.81
0.01
3.57
78
78
78
1.65
12.39
15.35
9.76
0.85
12.50
1.87
25.74
19.88
0.01
100.00
0.03
11
37.53
44.87
54.74
56.14
54.06
32.04
68.35
9.97
13.11
7.05
4.90
6.57
0.43
27.78
1.12
1.48
1.67
1.61
1.60
0.29
4.15
2.75
0.20
0.08
0.22
0.50
0.10
1.70
20.14
17.11
22.86
24.82
23.18
11.32
35.23
2.14
2.50
2.14
1.55
1.83
0.31
3.98
13.83
10.80
5.30
6.68
6.85
0.79
16.44
12.11
8.64
4.07
2.16
3.54
0.27
14.42
0.10
0.48
1.09
0.77
0.82
0.09
2.90
0.31
0.81
1.00
1.15
1.05
0.62
1.61
100.00
100.00
100.00
100.00
100.00
0.08
0.07
0.05
0.05
0.05
0.02
0.18
1
5
10
22
37
37
37
1. Wood and woody biomass (WWB)

Mean
22.22
Minimum
1.86
Maximum
68.18
Aquatic biomass
Marine macroalgae
Solid fossil fuels
Peat
Lignite (mean)
Sub-bituminous coal (mean)
Bituminous coal (mean)
Coal (mean)
Coal (minimum)
Coal (maximum)
the late winter [131]. Additionally, grass produced on a clay soil

contained almost ve times as much ash yield as a crop from a humus-rich soil, mainly due to differences in Si content [186]. It was
also found that elements such as Si plus Al, Ti and Fe normally represent inorganic matter of soil origin [70]. Finally, the ash yields of
ner fractions (<420 lm or < 180 lm) of biomass are substantially
larger than of coarser fractions (420850 lm or 1802000 lm)
[7,48].
The combustion temperature also signicantly affects the yield
of ash from biomass. For example, the reference investigations
show that ash yields determined at 10001300 C are 1070% lower than those produced by LTA at 100150 C or HTA at 500575 C
[48,60,68,89,94,183]. The present study (Table 4) conrmed the
above observations and reveals that the ash yields determined at
TiO2
11001500 C are 759% lower than those produced at 500 C,

namely MM (59%) > SS (44%) > WS (43%) > BC (39%) > CC
(33%) > PP (29%) > SG (19%) > RH (7%). This order shows that minimum losses occur for the biomass varieties highly enriched in silica
and silicates (RH and SG), while maximum losses are typical for
biomass varieties abundant commonly in Ca, Cl, Fe, K, Mg, Na, P,
S, chlorides, sulphates, carbonates and phosphates (Table 4 and
[2]). These weight losses for biomass are normally higher than
for coal and such differences are a result of some more intensive
phase transformations (loss of adsorbed and combined water, combustion of volatile matter, decomposition of less stable minerals)
and probably higher volatilization behaviour of mobile elements
(Br, C, Cl, H, Hg, K, N, Se, S and other trace elements) from biomass
phases in the high temperature ranges [163,164].
54
Table 6
Contents of some trace elements in eight biomass ashes (500 C/2 h), ppm.
Element
Coal ash
Clarkea
Walnut
shells
WS
Mean
EDFb
SG
Sunower
shells
SS
4101
7106
5900
8908
7857
23.5
13.0
19
33.6
35
31.7
54
25.1
278
27.4
64
23.0
145
2.5
1.8
66
167
42
160
466
64
348
1825
107
49
872
37
1504
365
574
167
202
60
384
1862
151
3.8
3.8
2.0
5.1
139
15.7
1232
5.0
36
9.8
52
3.5
636
10.5
779
8.2
76
35.3
103
9.8
66
37.1
103
4.4
331
19.0
338
5.9
477
28.9
110
5.9
232
21.6
366
4.9
2.5
2.5
2.6
1.91
0.32
0.90
0.16
1.00
0.20
4.13
0.62
3.37
0.73
1.98
0.30
2.57
0.52
2.12
0.40
3.5
18.2
Beech wood
chips
BC
Corn
cobs
CC
Marine
macroalgae
MM
Plum
pits
PP
Rice
husks
RH
Switchgrass
Non-metal elements
B
335
10,257
6619
8653
11,311
Lithophile elements
Be
9.4
Rb
79
20.9
453
23.4
233
8.7
25
Siderophile elements
Cr
100
Mn
490
Ni
76
24
10,595
36
750
404
286
Chalcophile elements (metals and semi-metals)

Cd
1.2
4.9
Cu
92
98
Se
8.8
16.4
Zn
140
213
Noble elements
Ag
0.61
Au
0.022
Sample
code
1.08
0.37
Note: The mineralogical classication of elements [173] was used.

a
Clarke for coal ashes worldwide [172].
b
Enrichment/depletion factor (EDF) is dened as a ratio of the element content in biomass ash to the respective Clarke value in coal ash.
(1) Positively and signicantly (at 95% condence level) with

pH, ash bulk density, electrical conductivity, dry water-soluble residue, S, N, Cl, hemicellulose, P2O5 and C; and positively and insignicantly with SiO2, extractives, cellulose, H
and SO3.
(2) Negatively and signicantly with volatile matter, Mn, O and
MgO; and negatively and insignicantly with lignin, xed C,
Fe2O3, K2O, Na2O, TiO2, Al2O3 and CaO according to the correlation analyses [1,2].
mass varieties belonging to the specied inorganic biomass types

and sub-types. Hence, some important associations can be identied for indicator purposes according the above correlations. For
example, natural biomass commonly enriched in hemicellulose,
water-soluble salts and silicic acid (authigenic phosphates, sulphates, chlorides, nitrates and opal) tends to produce higher ash
yields. Certainly, high ash yields in some non-biomass materials
can also be a result of incorporation of: (1) detrital (terrigeneous)
sand, soil or shell particles in natural biomass and (2) mineral
and metallic contaminants in semi-biomass (as mentioned above
and described in [1,2]).
The present study also shows that there are some interesting
relationships between the ash yield and detrital/authigenic index
(DAI), which is the ratio between the sum of Si + Al + Fe + Na + Ti
oxides and sum of Ca + Mg + Mn + K + P + S + Cl oxides (Fig. 3). It
should be noted that the common detrital position of Si and Na
in biomass (as quartz and acid plagioclases) can be changed to
the authigenic position in some biomass varieties due to enrichment of authigenic opal (rice husks, some grasses and straws)
and halite (olive husks and pits, algae or sea transport of biomass),
respectively [1]. Additionally, the two trends between the ash yield
and DAI specied in Fig. 3 illustrate the very high contents of authigenic inorganic matter for some biomass varieties highly enriched
in Si-bearing compounds (such as rice straw, rice husks, reed canary grass, coconut shells for the line up) and Ca- and P-bearing
components (namely, chicken litter and meat-bone meal for the
line below). On the other hand, some general and very strong positive correlations between Al, Fe and Ti in BA also occur (Fig. 3).
They indicate that most biomass varieties probably exhibit the effects of a general uptake of these elements as has been mentioned
earlier [108]. Therefore, such elements can be used as an indicator
of minerogenic contamination (by rock minerals in soil), while the
uptake of major nutrients (Ca, K, Mg, P and S) is closely related to
an optimal growth of the plant [188].
Additionally, sub-trends following dominantly the major positive or negative trends between ash yield and many characteristics
(particularly, N, S, Cl, cellulose, hemicellulose, extractives, SiO2,
CaO, K2O, P2O5, MgO, Al2O3, Na2O) can also be seen (Figs. 2 and
3). The reason for such sub-trends is mostly associated with bio-
3.1.5. Formation and behaviour

The numerous processes related to ash formation are listed in
Table 2. The detailed phase transformations during biomass combustion are beyond the subject of the present study and they will
Finally, it should be stated that the abnormally high ash yields

of biomass are commonly an indication of increased amounts of
contamination such as:
Soil added by heavy rainfall, dry and windy conditions mobilizing dust [177].
Soil added during harvesting processes and other biomass handling activities [177,184].
Mineral and metallic impurities and other contaminants due to
later manufacturing processes [1,2].
3.1.4. Correlation and association

The reference investigations show that there are some strong
correlations between ash yield and other characteristics,
namely:(1) Positive correlations with contents of Cl, N and S for
straws (consistent with a predominantly authigenic inorganic matter) [70]; Si [133]; N and S [187]; bark [180]; and Ca, P, S and Si
[131]; and(2) Negative correlations with concentrations of C, H,
O, N, Cl and S for woods (consistent with inorganic matter of
increasing detrital origin, namely greater levels of dirt) [70]; and
C, Cl and Na [131].
The present study (Figs. 2 and 3) shows that biomass ash yield
correlates:
55
% 100
FC (db)
60
10
20
30
50
H (daf)
30
10
10
10
30
10
20
30
40
35
30
25
20
5
10
15
20
60
40
30
10
15
20
25
60
40
10
20
30
10
20
30
10
20
30
10
10
20
30
SO3
10
20
Ash (db)
30
40
25
20
30
40
10
20
30
40
Ash (db)
%
100
10
1
0.1
0.01
0.1
20
10
10
10
15
Ash (db)
40
% 100
% 100
10
Ash (db)
Ash (db)
10
0.1
0
40
40
0
0
% 100
0.1
Ash (db)
MgO
10
40
15
10
20
0
0
% 20
% 100
25
20
Ash (db)
20
60
40
40
15
% 80
10
Ash (db)
20
20
30
K2O
60
CaO
80
20
% 100
80
30
Ash (db)
% 100
40
Ash (db)
40
50
30
60
40
20
25
Ash (db)
20
Ash (db)
Ash (db)
10
20
Ash (db)
%
40
10
0.1
Lignin (daf)
40
0.01
0.01
40
Cellulose (daf)
0.1
20
Ash (db)
10
30
0.1
0
20
Ash (db)
% 100
40
10
Extractives (daf)
30
S (daf)
40
15
Cl (db)
20
10
Hemicellulose
(daf)
30
0
10
Ash (db)
SiO2
20
Al2O3
O (daf)
40
P2O5
10
Ash (db)
20
Fe2O3
40
0
40
Ash (db)
60
N (daf)
80
40
20
Na2O
VM (db)
80
40
C (daf)
1
0.1
0.01
10
20
Ash (db)
30
40
10
20
Ash (db)
30
40
Fig. 2. Some correlations among the characteristics of 78 and 28 varieties of natural biomass based on [1,2], wt.%. Abbreviations: daf, dry, ash-free basis; db, dry basis; FC,
xed carbon; VM, volatile matter.
10
Mn
0.1
10
20
30
10
Ash (db)
20
30
%
TiO2
10
1
40
Ash (db)
% 100
Fe2O3
0.01
0
40
10
15
10
1
0.1
Al2O3
10
15
20
EC (mS/cm)
6
5.5
0
10
20
Ash (db)
30
0.1
10
100
Fe2O3
20
15
10
1
10
5
0
0.1
40
0.1
100
6.5
30
10
Al2O3
20
0.01
0
20
10
Ash (db)
0.01
0.1
1
0.1
0.01
0
pH
10
1
0.1
0.01
Ash density (kg/m3)
100
10
TiO2
TiO2
100
DWR
DAI
56
10
20
Ash (db)
30
10
20
Ash (db)
30
500
400
300
200
100
0
0
10
20
Ash (db)
30
Fig. 3. Some correlations among the characteristics of 78 and 8 varieties of natural biomass based on [1,2], wt.%. Abbreviations: DAI, SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2/
CaO + MgO + MnO + K2O + P2O5 + SO3; db, dry basis; DWR, dry water-soluble residue; EC, electrical conductivity.
be characterized in a further publication. The present study only

addresses some general observations on the ash formation and
behaviour of inorganic and organic matter during heating. These
preliminary observations are based on data obtained by optical
microscopy, XRD and DTA-TGA for eight biomass varieties and they
are summarised below.
Some processes such as: (1) fragmentation of particles (500 C);
(2) initial (700900 C), signicant (7001100 C) and extensive
(7001300 C) agglomeration of particles; (3) initial (700 C),
extensive (9001100 C) and complete (11001500 C) melting of
particles; (4) various new phase crystallizations (5001500 C);
and (5) glass formation (7001500 C); were observed microscopically in BAs.
The DTA-TGA proles of the biomass varieties studied show
very similar combustion behaviour for organic matter (OM) despite
their highly variable chemical and phase composition (Table 4). For
example, they reveal some common and similar transformations
such as: (1) loss of adsorbed water (5792 C); (2) OM oxidation
(200650 C); and (3) burning of some residual char (650800 C).
In contrast to biomass samples, the DTA-TGA proles of BAs
produced at 500 C/2 h show very distinct and complex transformation behaviour due to their highly variable inorganic composition (Table 4). For instance, they reveal: (1) loss of adsorbed
water (69129 C); (2) burning of the residual char (300850 C);
and (3) complex phase transformations related to decomposition
of various carbonates, sulphates and phosphates, formation of silicates and melting of phases up to 1300 C.
Typical XRD patterns (Fig. 4) of BC, water-soluble residue of BC

and BC ash treated up to 1300 C, as well as DTA-TGA proles
(Fig. 5) of BC and BC ash are given just for an initial illustration
of the future investigations. Different phase transformations related to organic matter, oxalates, calcite, quartz, whitlockite, portlandite, lime, periclase, apatite, glass and other phases and
minerals in biomass ashes can be seen on XRD patterns (Figs. 4
and 6).
As a result of biomass combustion, volatilization of elements
forming OM (C, H, N, S, O) or associated with OM (Ca, Mg, Na, K,
Fe, Si, Al, P, Ti, Mn, others) as covalently or ionically bound elements, organic-metal components, adsorbed ions or metal ions in
ion-exchanged forms bound to specic functional groups [2] occurs. These elements can: (1) escape the system as volatile components; (2) form discrete inorganic phases in ash; (3) react with
each other; or (4) react with original or newly formed inorganic
matter [163,164]. For example, the highly variable values of elements emitted during biomass combustion are listed in Table 7
based on reference investigations. It can be seen that elements
such as Hg > (Cd, Sb, Se, V) > Br > Cr > Pb > Zn > Cl > As > S > K > Na
show the highest volatilization potential (based on mean values)
[14,89,108,110,114,123,189192].
The reference investigations show that the size of biomass y
ash particles varies from 1050 nm to more than 12 mm, but
these powder materials are commonly very ne as their median
size is dominantly below 10100 lm [14,33,47,107,113,114,118,
126,191]. It was found in the above studies that the alkali chlorides
57
Fig. 4. XRD patterns of beech wood chips (BC), dry water-soluble residue (DWR) from BC and high-temperature ashes (HTAs) of BC generated at 500 C/2 h, 700 C/1 h,
900 C/1 h 1100 C/1 h and 1300 C/1 h. Abbreviations: Ap, apatite (Ca(PO4)3(Cl,F,OH)); Arc, arcanite (K2SO4); CaNH, Ca nitrate hydrate (Ca(NO3)2.2H2O); Cc, calcite (CaCO3);
Cps, counts per second; Ha, halite (NaCl); L, lime (CaO); Mu, mullite (Al6Si2O13); Op, opal (SiO2.nH2O); Peri, periclase (MgO); Port, portlandite (Ca(OH)2); Q, quartz (SiO2); Sy,
sylvite (KCl); Wd, weddelite (Ca(CO2)2.(H2O)2); Wh, whewellite (Ca(CO2)2.H2O); Wl, whitlockite (Ca3(PO4)2). The occurrence of Mu and Q in the sample BC-HTA-1300 is a
result of contamination from the broken ceramic crucible.
and sulphates and some trace elements (for example, Pb and Zn)
were normally enriched in the nest y ash fraction (<1 lm) originated from volatilized elements that nucleate to form new particles or condense on existing particles during the ue gas cooling.
On the other hand, the coarser ash fraction (>1 lm) is dominated
by components containing non-volatile elements such as Ca, Si,
Mg, Al, Fe, P and Mn that have remained in the solid and/or liquid
phases during the combustion process [14,118,191]. It was also
identied that Ca-bearing minerals seemed to be enriched commonly in the size range 150 lm, while Si-bearing minerals were
normally found in the largest particles (>1050 lm) [47,107].
Finally, the present study indicates some important combustion
trends. It was found that the organic matter of different biomass
varieties tends to show similar combustion behaviour, whereas
the inorganic matter of these biomass varieties has a tendency to
reveal variable performance during burning. The preliminary
observations also indicate that the thermal behaviour of different
biomass ashes tends to be similar among the inorganic S, C,
K and CK types and probably some sub-types specied recently

[1,2]. The interesting behaviour of inorganic and organic matter
during combustion will be characterized in a further publication.
3.1.6. Fusion temperatures
The ash-fusion temperatures (AFTs), namely initial deformation
(DT), spherical (ST), hemispherical (HT) and uid (FT) temperatures of 87 varieties of biomass are given in Table 8 based on
numerous references [10,14,25,29,30,35,41,45,48,62,68,69,77,80,
81,86,90,99,129,133,177,181,193201]. AFTs of coals with different rank [170] are also provided in Table 8 for comparison. These
data show that biomass ashes have more variable AFTs in comparison with coal ashes (Table 8). Therefore, the AFTs values for 77
varieties of biomass were subjected to a correlation test to calculate correlation coefcient (R2) values among these four characteristic temperatures. Ten biomass varieties (samples 5, 12, 18, 24, 31,
48, 52, 53, 80 and 81) were excluded from the database due to
incomplete data for the most important DT, HT and FT (Table 8).
58
Fig. 5. DTA and TGA proles of beech wood chips (BC) and high-temperature ash
(HTA) of BC generated at 500 C/2 h.
It was found that there are signicant, positive and very strong R2
values among AFTs, namely for:
(1) DT with ST (0.78) > HT (0.53) > FT (0.50).
(2) ST with HT (0.84) > FT (0.82).
(3) HT with FT (0.97); as the signicant R2 values at 95% condence level are P0.22 and P0.27 for 77 and 51 variables,
respectively.
Hence, there is an almost perfect t for both HT and FT, while ST
and especially DT show more individual behaviour probably due to
some different processes responsible for the specic AFTs. It should
be noted that such very similar correlations were also identied for
coal AFTs [202,203]. These observations indicate that the major
processes responsible for the characteristic AFTs seem to be similar
for both biomass and coal ashes.
The present study shows that the DT value of biomass ashes
(Table 8) varies over the large interval of 6701565 C (mean
1111 C). In contrast, DT value of coal ashes (Table 8) is in the relatively more narrow range of 11051525 C (mean 1251 C). The
mean DT value decreases in the order: bituminous coal > sub-bituminous coal > wood and woody biomass > contaminated biomass > lignite > herbaceous and agricultural biomass (Table 9).
Hence, DT mostly has a much lower value in biomass ash than in
coal ash. The low DT is characteristic of some biomass sub-groups
such as herbaceous and agricultural shells, straws, grasses, stalks
and other residues, as well as wood and woody stumps. The extremely low DT is typical of some biomass varieties, namely eupatorium and xanphium stumps, alfalfa, safower and wheat-barley
straw. In contrast, the high DT is characteristic of some biomass

sub-groups such as agricultural husks and wood and woody barks
and stems. The exceptionally high DT is typical of some biomass
varieties, namely balsam, hemlock, poplar and maple (hard) barks,
rice husks, willow stems and reed canary grass.
The present study reveals that the ST value of biomass ashes
1277 C). The mean ST value decreases in the order: wood and
woody biomass > herbaceous and agricultural biomass (Table 9).
The low ST is characteristic of some biomass sub-groups such as
herbaceous and agricultural shells, straws, grasses, stalks and other
residues, similar to DT. The extremely low ST is typical of some biomass varieties, namely almond shells, wheat straw, thistle and
miscanthus. In contrast, the high ST is characteristic of some biomass sub-groups such as wood and woody barks, twigs, stems
and leaves. The exceptionally high ST is typical of some biomass
varieties, namely balsam, maple (hard), beech, poplar and hemlock
barks, as well as spruce and willow stems and reed canary grass.
The present study shows that the HT value of biomass ashes
1322 C). In contrast, HT value of coal ashes (Table 8) is in the relatively more narrow range of 12001575 C (mean 1388 C). The
mean HT value decreases in the order: bituminous coal > wood
and woody biomass > sub-bituminous coal > contaminated biomass > lignite > herbaceous and agricultural biomass (Table 9).
Hence, HT normally has a lower value in biomass ash than in coal
ash. The low HT is characteristic of some biomass sub-groups such
as herbaceous and agricultural straws, stalks, pits, grasses, shells
and other residues. The extremely low HT is typical of some biomass varieties, namely wheat-barley, barley, oat and rye straws,
corn cobs and grass. In contrast, the high HT is characteristic of
some biomass sub-groups such as agricultural husks and wood
and woody barks and twigs. The exceptionally high HT is typical
of some biomass varieties, namely spruce stems, rice husks, balsam
and maple (hard) barks, tree pruning, alfalfa and reed canary grass.
The present study reveals that the FT value of biomass ashes
(Table 8) varies over the large interval of 1000 >1700 C (mean
1353 C). In contrast, FT value of coal ashes (Table 8) is in the relatively more narrow range of 12051585 C (mean 1411 C). The
mean FT value decreases in the order: bituminous coal > wood
and woody biomass > sub-bituminous coal > lignite > herbaceous
and agricultural biomass > contaminated biomass (Table 9). Hence,
FT normally has a lower value in biomass ash than in coal ash. The
low FT is characteristic of some biomass sub-groups such as herbaceous and agricultural straws, stalks, shells, grasses, pits and other
residues, similar to HT. The extremely low FT is typical of some
biomass varieties, namely corn cobs, stalks and fodder, banagrass,
wheat-barley and barley straws, paper pellets, grass and cynara
grass. In contrast, the high FT is characteristic of some biomass
sub-groups such as agricultural husks and wood and woody barks
and twigs, similar to HT. The exceptionally high FT is typical of
some biomass varieties, namely spruce and willow stems, balsam,
beech, hemlock, maple (hard), pine, poplar and spruce barks, as
well as tree pruning, rice husks, reed canary grass, alfalfa, sugar
cane baggase and paper sludge.
The present study shows that AFTs of biomass are more variable
than of coal and they are normally lower (excluding some lignites
and certain biomass varieties from S and C ash types). For comparison, BAs can be divided initially into ve melting types according to HT (the most informative AFT), namely:
(1)
(2)
(3)
(4)
(5)
Very low (<1000 C).

Low (10001200 C).
Moderate (12001400 C).
High (14001600 C).
Very high (>1600 C) types; similar to coal ashes [152].
59
Fig. 6. XRD patterns of high-temperature ashes (HTAs) generated from eight biomass varieties at 500 C/2 h. Abbreviations: A, anhydrite (CaSO4); Ap, apatite (Ca(PO4)3
(Cl,F,OH)); Arc, arcanite (K2SO4); BC, beech wood chips; Cc, calcite (CaCO3); CC, corn cobs; Cps, counts per second; Cr, cristobalite (SiO2); F, fairchildite (K2Ca(CO3)2); G,
gypsum (CaSO42H2O); Ha, halite (NaCl); K, kalicinite (KHCO3); KF, K feldspars (KAlSi3O8); MM, marine macroalgae; N, natrite (Na2CO3); NF, natrofairchildite (Na2Ca(CO3)2);
Pm, picromerite (K2Mg(SO4)26H2O); Pl, plagioclases (NaAlSi3O8CaAl2Si2O8); PP, plum pits; Q, quartz (SiO2); RH, rice husks; SG, switchgrass; SS, sunower shells; Sy, sylvite
(KCl); Tr, tridymite (SiO2); Wl, whitlockite (Ca3(PO4)2); WS, walnut shells.
Table 7
Mean and range values of elements volatilized during biomass combustion, wt.%.
Element
Mean
Minimum
Maximum
Samples
Reference used
Hg
Cd
Sb
Se
V
Br
Cr
Pb
Zn
Cl
As
S
K
Na
99
95
95
95
95
85
75
71
70
66
58
57
36
13
95
100
80
70
40
3
15
25
7
5
2
90
80
100
95
100
90
90
90
24
5
1
1
1
1
2
2
5
7
9
2
15
8
2
[108,192]
[108]
[108]
[108]
[108]
[108]
[108]
[190,191]
[190,191]
[14,114,123,189191]
[108]
[14,89,108,114,123,190,191]
[89,110,190,191]
[191]
60
Table 8
Ash-fusion temperaturesa of 87 varieties of biomass and coals with different rank, C.
Ash
1. Wood and woody biomass (WWB)
Mean
Minimum
Maximum
1.1. Stems (WWS)
1. Beech wood
2. Citrus tree wood
3. Cork oak
4. Eucalyptus
5. Eucalyptus stems
6. Fir-pine chips
7. Manzanita chips
8. Olive tree wood
9. Pine
10. Pine chips
11. Pine sawdust
12. Poplar
13. Rockrose
14. Sida rhombifolia stumps
15. Spruce
16. Spruce sawdust
17. Spruce wood
18. Spruce-pine pellets
19. Willow
20. Wood chips
Mean
DT
ST
HT
FT
1192
670
1565
1328
1105
1571
1380
1190
1665
1407
1207
>1700
1140
1210
1190
1155
1430
1236
1080
1225
1190
1125
1215
>1400
1360
1170
1320
1120
1225
1241
1453
1050
1227
1260
1240
1200
1200
1310
1295
1220
1215
1340
1335
1280
1245
1244
1270
1200
1210
1241
1246
1400
1325
1220
1250
1252
1249
>1400
1360
1280
1275
1271
1360
1310
1525
1150
1525
1370
1398
1600
1200
1665
1390
1439
1650
1270
>1700
1518
1297
1528
1190
1334
1550
>1190
1366
Typeb
Samplesc
M
L
VH
50
50
50
M
M
M
M
PH
M
M, H
M
M
M
M
PH
M
M
H
L, M
VH
PM
H
L
M
1
1
1
2
1
1
1
1
1
1
2
1
1
1
1
1
3
7
3
1
20
[14]
[62]
[197]
[197]
[35]
[30]
[68]
[62]
[197]
[196]
[77,196]
[197]
[197]
[201]
[198]
[195]
[14]
[29]
[194,196,198]
[68]
1
1
3
1
1
1
1
1
3
1
1
6
1
13
[68]
[68]
[68,196]
[25]
[90]
[68]
[68]
[68]
[68,196]
[68]
[35]
[14,68,196]
[68]
Reference used
1.2. Barks (WWBA)

21. Balsam bark
22. Beech bark
23. Birch bark
24. Coniferous bark-wood chips
25. Eucalyptus bark
26. Hemlock bark
27. Maple (hard) bark
28. Maple (soft) bark
29. Pine bark
30. Poplar bark
31. Sawmill bark
32. Spruce bark
33. Tamarack bark
Mean
1565
1360
1309
1100
1200
1471
1454
1387
1231
1471
1160
1345
1232
1330
1571
1538
1392
1574
1541
1440
1515
1548
1465
1425
1537
1250
1521
1551
1468
1519
1540
1576
1543
1487
1475
1275
1526
1554
1471
1527
1543
1474
1260
1473
1520
1274
1473
1530
1287
1483
H
H
H
H
M
H
H
H
H
H
PL
H
M
H
1.3. Stumps (WWST)

34. Anisomales stumps
35. Eupatorium stumps
36. Sida stumps
37. Vinca rosea stumps
38. Xanphium stumps
Mean
740
670
760
1191
670
806
1250
1109
1360
1314
1105
1228
1412
1233
1460
1421
1191
1343
1441
1242
1490
1462
1207
1368
H
M
H
H
L
M
1
1
1
1
1
5
[181]
[181]
[181]
[201]
[181]
1.4. Leaves (WWL)

39. Parasol tree leaves
40. Sida rhombifolia leaves
41. Vinca rosea leaves
42. Vine shoots
Mean
1126
1081
1182
1268
1164
1292
1245
1327
1280
1286
1294
1330
1429
1353
1352
1295
1388
1471
1380
1384
M
M
H
M
M
1
1
1
2
4
[77]
[201]
[201]
[45,62]
1.5. Twigs (WWT)

43. Sida rhombifolia branches
44. Vinca rosea branches
Mean
1157
1180
1169
1335
1320
1328
1434
1409
1422
1474
1456
1465
H
H
H
1
1
2
[201]
[201]
1.6. Roots (WWR)

45. Sida rhombifolia roots
46. Vinca rosea roots
Mean
1073
1155
1114
1196
1280
1238
1305
1390
1348
1354
1435
1395
M
M
M
1
1
2
[201]
[201]
1.7. Others (WWO)

47. Forest residue
48. Olive tree prunings
49. Tree pruning
50. Wood residue chips
Mean
1320
1280
770
1175
1136
1380
1395
>1400
>1550
1250
P1399
M
PM
H
M
M
1
1
1
1
4
[45]
[197]
[68]
[196]
1205
1205
1550
1230
1387
61

Table 8 (continued)
Ash
DT
2. Herbaceous and agricultural biomass (HAB)

Mean
979
Minimum
700
Maximum
1472
2.1. Grasses and owers (HAG)
51. Alfalfa
52. Banagrass
53. Brassica
54. Cynara grass
55. Grass
56. Miscanthus
57. Reed canary grass
58. Safower
59. Thistle
Mean
2.2. Straws (HAS)
60. Barley straw
61. Bean straw
62. Oat straw
63. Rice straw
64. Rye straw
65. Wheat straw
66. Wheat-barley straw
Mean
ST
1112
795
1513
700
1005
1060
953
940
1453
700
945
970
1023
990
1513
980
1127
FT
Typeb
Samplesc
1241
975
1605
1285
1000
P1620
M
VL
VH
34
34
34
1550
1130
1090
1168
1549
1430
1240
1308
>1550
1000
>1400
1180
1165
1240
P1586
>1430
P1275
P1314
H
VL
PM
L
L
L
H
H
M
M
1
4
2
1
4
2
14
1
2
9
1125
>1205
1200
1369
1350
1226
1025
1214
L
M
L
M
L
L
VL
L
2
2
1
9
1
9
1
7
[10,68]
[68]
[10]
[30,48,68,77,90,197]
[10]
[10,14,48,80,99,194,197,200]
[25]
HT
Reference used
[68]
[193]
[197]
[177]
[14,198]
[14]
[129,133]
[68]
[197]
845
920
800
991
825
915
700
857
1061
1025
1205
1050
1266
1100
1111
975
1105
2.3. Stalks (HAST)

67. Corn stalks
68. Cotton stalks
69. Pepper stalks
Mean
973
1019
1154
1049
1159
1202
1181
1155
1288
1224
1222
>1155
1335
1241
P1244
L
M
M
M
3
2
1
3
[68]
[68,80]
[80]
2.4. Shells (HASH)

70. Almond shells
71. Walnut shells
Mean
775
820
798
1395
1225
1310
>1400
>1225
>1313
M
M
M
4
1
2
[68,197]
[68]
1605
P1620
VH
[68,69,86,90]
1265
1303
1328
[41,45,62,68,197]
1280
1310
1020
1180
1380
1180
1310
1330
>1020
>1180
>1380
1190
1325
1360
1145
1260
1238
1500
1390
1200
>1260
P1278
M
L
L
M
L
M
PL
H
M
L
M
M
1
1
1
1
1
2
1
6
1
3
1
11
[81]
[68]
[68]
[68]
[45]
[197]
[199]
[193]
[197]
[14]
[68]
1205
1130
1505
1280
1130
1505
1210
>1130
1510
P1283
>1130
1510
M
L
H
M
L
H
1
1
1
3
3
3
[45]
[68]
[45]
2.5. Husks (HAH)

72. Rice husks
1472
2.6. Pits (HAP)

73. Olive pits
1132
1180
941
795
798
2.7. Other residues (HAR)

74. Cocoa (shea) meal
75. Corn cobs
76. Corn fodder
77. Cotton gin trash
78. Cotton residue
79. Olive residue
80. Palm kernel expellers
81. Sugar cane baggase
82. Sunower
83. Wheat cereals
84. Wheat straw-corn stalks
Mean
740
990
985
1023
3. Contaminated biomass (CB)

85. Demolition wood
86. Paper pellets
87. Paper sludge
Mean
Minimum
Maximum
1195
890
1438
1174
890
1438
All varieties of biomass (AVB)

Mean
Minimum
Maximum
1111
670
1565
1277
795
1571
1322
975
1665
1353
1000
>1700
M
VL
VH
87
87
87
Natural biomass (NB)

Mean
Minimum
Maximum
1109
670
1565
1277
795
1571
1323
975
1665
1356
1000
>1700
M
VL
VH
84
84
84
Coal
Lignite (mean)
Subbituminous coal (mean)
Bituminous coal (mean)
Coal (mean)
1147
1218
1280
1251
1261
1365
1404
1388
1286
1389
1423
1411
M
M
H
M
5
10
22
37
1140
900
1010
1010
1120
1260
1070
1020
1150
[170]
[170]
[170]
[170]
(continued on next page)
62
Table 8 (continued)
Ash
Coal (minimum)
Coal (maximum)
a
b
c
DT
1105
1525
ST
HT
1200
1575
FT
1205
1585
Typeb
Samplesc
Reference used
L, M
H
37
37
[170]
[170]
DT, initial deformation temperature; ST, spherical temperature; HT, hemispherical temperature; FT, uid temperature.
Melting types based on HT: VL, very low (<1000 C); L, low (10001200 C); M, moderate (12001400 C); H, high (14001600 C); VH, very high (>1600 C) types.
Some of these data are mean values from numerous determinations for a given biomass variety.
Some indicative inorganic trends of natural biomass in comparison with coal were found recently [2], namely the potential of biomass to have normally:
(1) Higher values of Ca, Cl, H, K, Mg, Mn, Na, O, P, carbonates,
chlorides, phosphates, organically bound inorganic elements
and water-soluble components.
(2) Lower values of Al, C, Fe, N, S, Si, Ti, ash (inorganic matter),
oxyhydroxides, silicates and sulphates-sulphides.
These differences could be the reason for the lower AFTs of biomass in comparison with coal (Tables 8 and 9). For example, it is
widely accepted that high contents of Si-, Al- and Ti-bearing minerals are responsible for increased AFTs of coal [152]. An understanding of such differences, in particular for the various
inorganic and AFT types and sub-types, is important for troublefree combustion and co-combustion of biomass with coal and
other fuels (see Part 2). The phase transformations responsible
for the specic AFTs during biomass combustion are beyond the
subject of the present study and they will also be characterized
in a future publication.
3.1.7. Leaching
3.1.7.1. Water leaching. The reference investigations show that the
content of water-soluble fraction in BA is high [14,69] and can be
up to 61.0% [103], while the same value for coal ashes is much less,
namely 0.27.2% (mean 1.6%) [150]. The pH values of the different
BA leachates (dominantly produced from woody and straw biomass) vary in the range 4.513.4 (mean about 10.7)
[14,24,39,41,45,47,57,60,105,121,132,204], while the values of
water leachates from coal ashes fall in a more narrow range,
namely 6.212.5 (mean 10.0) [150]. The pH values of woody BAs
are normally higher than straw and cereal BAs due to the higher
Ca and lower S and Cl concentrations in the former ashes [14]. It
is well known that in comparison with coal and peat, biomass
has signicantly higher levels of water-soluble material abundant
in K, Cl, Ca and Mg [14,69]. Therefore, the loss of organic acids during biomass burning and the production of soluble Ca, Mg, K and
Na oxides, hydroxides, carbonates and bicarbonates in BA are the
major reasons for increasing pH in BA [60,105,121]. The pH of
BAs is also largely inuenced by the combustion temperature
and the storage time, as the alkalinity decreases with increasing:
(1) combustion temperature and (2) period of storage [121]. The
decreasing trend for pH with storage time can be caused by transformation of hydroxides to carbonates in BA [24]. It was also found
that the total dissolved solids from wood BA increased by 500% as
the pH decreased from 13 to 5, while their extraction rate was
essentially independent of pH [60].
The reference investigations also reveal (Table 10) that the
mean contents of the water-soluble elements leached from different BAs (produced mainly from woody and straw biomass) are:
Cl > S > K > Na > Sr > Ni > Mn > Cd > Cr > Zn > Co > Si > Mo > Li > (Mg, Pb) > Ca > Cu > Ba > P > Se > Sb > Al > Fe > (Br, Hg) > (As, B,
Sn, Ti, V) [18,24,35,41,45,57,60,65,67,70,95,121,122,137,157]. It is
widely accepted that the solubility (hence, environmental mobility) of most elements contained in BAs and coal ashes is markedly
pH sensitive and a more alkaline character depresses the release of

a large number of elements (Al, Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb, Sn Ti,
Zn among others) but enhances the release of oxyanionic-forming
species of As, B, Cr, F, Mo, Sb, Se, V and W [23,204206].
The data from Table 3 show that the water-soluble phases in BA
mostly include phases of alkali and alkaline earth elements such
as:
(1) Highly soluble chlorides (sylvite, halite), sulphates (arcanite,
syngenite, ettringite, gypsum), oxides (lime), hydroxides
(portlandite), nitrates, carbonates and bicarbonates.
(2) Certain less soluble carbonates (calcite) and phosphates
(phosphorites).
(3) Some slightly soluble phosphates (apatite) and silicates (Ca
silicates, feldspars).
It should be stated that some precipitation of minerals such as
ettringite, portlandite, calcite, gypsum and Ca silicate hydrate from
water leachates of BAs at alkaline pH (typical for BA) was also observed [57,60]. It is well known that there is transformation of elements from water-soluble forms in the biomass itself to more
stable acid soluble and insoluble forms (silicates and oxides) in
BAs [18]. Hence, the conditions under which the biomass is burned
are also important for the amount and properties of the water-soluble fraction in BA. For example, carbonates and bicarbonates produced at combustion temperatures below 500800 C are
common, while oxides and silicates are most prevalent at higher
temperatures (at or above 8001000 C) and longer heating times
[25,60,62,107,207].
Finally, the dry residues obtained by the evaporation of watersoluble extracts from solid fuels and their ashes are quite important for the denitive identication of various chlorides (sylvite,
halite, carnallite), sulphates (gypsum, bassanite, anhydrite, hexahydrite, barite, alunite, jarosite, szomolnokite, kieserite, polyhalite), carbonates (calcite, dolomite, ankerite), silicates (opal,
zeolite), hydroxides (portlandite), organic minerals (Ca oxalates),
phosphates and amorphous matter that may be originally present.
These water-soluble residues can be highly enriched in some mobile minerals and minor and trace elements (B, Cl, Cs, Cu, Li, Mn,
Mo, Ni, P, Rb, Sb, Se, Sn, Sr, Ti, Zn, others) and most of them may
have resource potential and/or be of environmental concern during
the transport, storage and processing of solid fuels and their ashes
(see Part 2 and [145,146] and references therein). Some initial
investigations about the composition and signicance of watersoluble residues produced from biomass have been described recently [2].
3.1.7.2. Leaching by different solvents. In contrast to the simple and

highly informative water leaching of BA, the leaching of BA by
other solvents is accompanied by serious problems and some elucidation of this method is required. Therefore, a short summary of
leaching of solid fuels and their ashes by different solvents is included herein, based on ([145,146] and references therein). There
are numerous more or less successful leaching procedures using
open or closed systems for dissolving (or etching) organic matter
and inorganic matter from solid fuels and their ashes. The digestion
Abbreviations: AVB, all varieties of biomass; B, bituminous coal; C, coal; CB, contaminated biomass; DT, initial deformation temperature; FT, uid temperature; HAB, herbaceous and agricultural biomass; HAF, herbaceous and
agricultural bers; HAG, herbaceous and agricultural grasses and owers; HAH, herbaceous and agricultural husks; HAP, herbaceous and agricultural pits; HAR, other herbaceous and agricultural residues; HAS, herbaceous and
agricultural straws; HASH, herbaceous and agricultural shells; HAST, herbaceous and agricultural stalks; HT, hemispherical temperature; L, lignite; NB, natural biomass; S, sub-bituminous coal; ST, spherical temperature; WWB,
wood and woody biomass; WWBA, wood and woody barks; WWL, wood and woody leaves; WWO, other wood and woody biomass; WWR, wood and woody roots; WWS, wood and woody stems; WWST, wood and woody stumps;
WWT, wood and woody twigs.
FT
HT
HAH(1472) > WWBA(1330) > B(1280) > C(1251) > WWS(1227) > S(1218) > WWB(1192) > CB(1174) > WWT(1169) > WWL(1164) > L(1147) > WWO(1136) > HAP(1132) > WWR(1114) > AVB(1111)
> NB(1109) > HAST(1049) > HAR(1023) > HAB(979) > HAG(970) > HAS(857) > WWST(806) > HASH(798)
WWBA(1473) > WWB = WWT(1328) > WWS(1297) > WWL(1286) > AVB = NB(1277) > HAP(1265) > WWR(1238) > WWST(1228) > WWO(1205) > HAST(1181) > HAR(1150) > HAG(1127) > HAB(1112) > HAS(1061)
> HASH(795)
HAH(1605) > WWBA(1473) > WWT(1422) > B(1404) > C(1388) > WWO(1387) > WWB(1380) > S(1365) > WWL(1352) > WWR(1348) > WWST(1343) > WWS(1334) > NB(1323) > AVB(1322) > HASH(1310) > HAG(1308)
> HAP(1303) > CB(1280) > L(1261) > HAB(1241) > HAR(1238) > HAST(1222) > HAS(1105)
HAH(1620) > WWBA(1483) > WWT(1465) > B(1423) > C(1411) > WWB(1407) > WWO(1399) > WWR(1395) > S(1389) > WWL(1384) > WWST(1368) > WWS(1366) > NB(1356) > AVB(1353) > HAP(1328)
> HAG(1314) > HASH(1313) > L(1286) > HAB(1285) > CB(1283) > HAR(1278) > HAST(1244) > HAS(1214)
DT
ST
Order for groups and sub-groups

AFT
Table 9
Decreasing orders of mean values for the ash-fusion temperatures (AFT) of the biomass groups and four solid fossil fuel types (bold font), as well as biomass sub-groups, C.
63
of organic constituents is commonly performed in hydrogen peroxide, concentrated nitric acid, alkaline hydroxides and organic solvents (for example, benzene and many others [2]). On the other
hand, the leaching of inorganic matter, specic mineral classes
and occasionally (for more simple systems) mineral groups and
species, is mostly carried out in acids. This demineralization is carried out mainly with hydrochloric, nitric and hydrouoric acids, to
a lesser extent, sulphuric, citric and acetic acids, and occasionally
other solvents such as ammonium acetate, Na acetate, Na hydroxide and hydroxylamine hydrochloride or their combination. However, the interpretation of such chemical leaching should always
be approached with much caution because the results obtained
are indirect. Additionally, this method is unselective and unreliable
for characterization of phases in multicomponent systems such as
solid fuels and their ashes because the solvents leach assumed and
preliminary unidentied components (various phases of Al, C, Ca,
Fe, K, Mg, N, Na, P, S, Si, Ti and trace elements) associated with both
organic matter and inorganic matter. Most of the unstable minerals
and phases in the samples treated by the specic solvents are normally easily leached, destroyed or altered during this procedure
(chlorides, sulphates, sulphides, carbonates, oxyhydroxides, phosphates and some silicates, glass and organic matter). Therefore,
the leached species are not available or actual for any future direct
phase study of the samples. On the other hand, there is a formation
of new articial and stable minerals and phases (some chlorides,
uorides, nitrates, oxalates, sulphates, oxyhydroxides, others), as
well as sorption phenomena (re-adsorption) of elements on some
stable phases in the system during this leaching and they can remain in the solid residue. Furthermore, portions of different original phases (quartz, clays, carbonates, oxides, phosphates, accessory
minerals, organic matter, others) treated by the above solvents
may remain insoluble in the solid residue. This is due to the lower
solubility of these phases or less accessability of other phases,
namely when the solvents cannot make contact with phases
encapsulated in other more stable organic and inorganic matrices
(in particular glass and certain silicates and oxides). There are also
many additional problems related to the appropriate selection of
conditions (time, temperature, agitation, batch or column test),
solvents, sample volume and particle size, solid/liquid ratio and
concentration and performance of the reagents because this selection can be different for each sample or type of samples due to variable composition. Finally, it should be stated that there are no
universal solvents and procedures for all solid fuels and their ashes
because each have distinct composition and behaviour during
leaching. Hence, the assumed dissolution of inorganic matter, organic matter and specic mineral classes, groups and species with
subsequent determination of the element contents in the leachates
should always be accompanied by phasemineral investigations on
the solid residues after chemical leaching. Unfortunately, such parallel investigations are not common in the literature.
3.1.7.3. Sequential leaching. A short summary of sequential chemical leaching (also known as sequential speciation, fractionation,
selective extraction and stepwise or successive leaching) of solid
fuels and their ashes by different solvents is also included herein,
based on ([145,146,208210] and references therein). This sequential leaching, using also open or closed systems, is commonly conducted by distilled, redistilled or deionised water (occasionally
plus acetic acid), hydrogen peroxide, acetic acid, ammonium acetate, hydrochloric acid, hydrouoric acid and nitric acid under different leaching schemes. These batch or column procedures use
sequential solubility in increasingly aggressive solvents for isolation of water-soluble, adsorbed and ion-exchangeable components, chlorides, sulphates, carbonates, oxides, phosphates,
silicates, glass, sulphides and organic matter. However, it was concluded that the utilization of sequential leaching methods without
64
Table 10
Mean and range contents of water-soluble elements leached from biomass ashes, wt.%.
Element
Mean
Minimum
Maximum
Samples
Reference used
Cl
S
K
Na
Sr
Ni
Mn
Cd
Cr
Zn
Co
Si
Mo
Li
Mg
Pb
Ca
Cu
Ba
P
Se
Al
Sb
Fe
Br
Hg
As
B
Sn
Ti
V
67.9
58.2
44.0
35.5
15.0
9.8
9.6
8.3
8.0
7.9
7.8
6.2
6.1
5.0
3.8
3.8
3.4
3.1
3.0
2.3
2.0
0.9
0.6
<0.1
Trace
Trace
0
0
0
0
0
8
16
2
0
99
97
98.1
100
0
0
0
0
0
0
0
Trace
18
46
48.9
30
44
15
74
12
0
Trace
0
0
39
15
19.7
10
15
0
Trace
0
9
1
1
17
14
26
22
1
4
7
6
5
8
4
13
2
1
17
5
19
8
1
15
1
13
2
14
1
1
1
1
1
12
1
[18,95,122,157]
[95,122,157]
[18,24,35,57,60,65,95,121,122,157]
[24,35,57,60,95,122,157]
[157]
[41,45,157]
[41,45,57,65,157]
[57,65,67,121,157]
[41,45,121,157]
[41,45,57,65,121,157]
[41,45,157]
[70,122,157]
[137,157]
[157]
[35,57,65,122,157]
[41,57,65,121,157]
[57,65,95,122,157]
[41,45,57,65,121,157]
[157]
[18,95,122,157]
[157]
[65,122,157]
[137,157]
[57,122,157]
[137]
[57]
[157]
[157]
[157]
[122,157]
[157]
signicant phasemineral information for the bulk samples and

each residue obtained, might be quite confusing in the interpretation of assumed leachates (see also Section 3.1.7.2). Unfortunately,
such combined investigations are not common in the literature.
Similarly, sequential chemical leaching of BA and biomass involves the treatment with a series of progressively more severe
chemical reagents in order to determine the speciation (chemical
forms, modes of occurrence) of elements. The chemical fractionation techniques of BA and biomass is normally performed by
deionised (or distilled) water, acidied water, ammonium
acetate, hydrochloric acid and occasionally other solvents
[14,18,35,36,38,39,48,64,65,6769,75,90,92,93,100,107,109,110,122,
177,179,190,204,205,211226]. Unfortunately, this approach is
mostly used to distinguish the speciation of elements in BA and
biomass. For example, as a result of this sequential solubility in
three increasingly aggressive solvents (water, ammonium acetate
and hydrochloric acid), the following speciation of elements was
identied in BA and biomass:
(1) Water soluble: salts; alkali salts; K, Cl and P; alkali material;
alkali metal salts; salts and loosely bound material; alkali
metal salts, S and Cl compounds; alkali chlorides, sulphates
and carbonates; chlorides and alkali sulphates and carbonates; alkali and alkaline earth chlorides and alkali sulphates;
alkali chlorides, sulphates and carbonates, and alkaline earth
chlorides.
(2) Ammonium acetate soluble: alkali material; ion-exchangeable material; organically associated metals; organically
associated components; ion-exchangeable elements and
organic acids; organic fraction present as cations and chelates; ion-exchangeable alkali and alkaline earth components; inorganic elements ionically bound to organic
structure; ion-exchangeable Ca, Na and K directly bound to
the organic groups; ion-exchangeable S and Ca and more
organically associated K and Na; ion-exchangeable inorganic
part represented by organically associated metal ions; and

organically associated ion-exchangeable Na, Ca and Mg,
and part of calcite.
(3) HCl soluble: carbonates and clays; carbonates and sulphates; Ca carbonates and sulphates; Ca and Fe carbonates
and Ca oxalates; carbonates, sulphates and mono-sulphides;
carbonate, sulphate and alkali chloride minerals; alkaline
earth carbonates, sulphates and sulphides; and inorganic
salts or organically associated non-metals like P or S.
(4) Solid residue with insoluble: silicates; silicate minerals;
principally silicates; quartz, clays and rutile; silicates, oxides
and sulphides; silica, silicates and other mineral species; silicates, oxides, sulphides and other minerals; silicates and S,
Cl and P covalently bound to the organic structure; and silicates and elements that are bound to organic matrix with a
covalent bond [14,36,38,48,90,92,109,190,211,215,220
222,225].
The above investigations obviously show that there was no one
real speciation among thousands of mineral species and phases or
even among a group of mineral species and phases. Hence, this
procedure cannot be applied to identify the actual modes of element occurrence in a multicomponent system and its advanced
role is highly overestimated in the literature. This was evident even
after the application of an improved six-stage sequential leaching
procedure (by distilled water, hydrogen peroxide and acetic,
hydrochloric, hydrouoric and nitric acids) of coal ashes with preliminary well known bulk chemical and phasemineral composition [209,210]. The sequential leaching and digestion by different
solvents as mentioned above (see also Section 3.1.7.2) have numerous limitations and these subsidiary procedures cannot be used as
basic techniques unaccompanied by other indispensable methods
of investigations such as light microscopy, electron microscopy,
XRD, physical separations and others. Hence, this indirect, rather
unselective and maybe unreliable sequential leaching procedure
cannot be applied to identify the actual modes of element occurrence in a multicomponent system such as biomass ash and the
interpretation should always be approached with much caution.
The results from the leaching procedures of muticomponent systems such as solid fuels and their ashes could be used mostly to
provide:
Determination of elemental proportions leached by specic solvents or their combination.
Preliminary information for some possible associations of elements in some mineral classes or group of phases.
Specication of some limiting and guiding values for certain
hazardous elements in leachates.
Simulations of some probable release of elements and assumed
components in time during weathering.
Experiments related to recovery or concentration of elements
and compounds for industrial purposes; as the results should
be interpreted very carefully and only together with data from
more secure methods.
Other preferably direct methods commonly applied for coal and
coal products ([145,146,208] and references therein) provide much
better information for such a speciation purpose and they should
always be used additionally before and after the supplementary
leaching procedures. Unfortunately, such parallel investigations
are almost absent among the extensive investigations related to
sequential leaching of solid fuels and their ashes.
3.2. General comments about phasemineral composition of biomass
ash
The reference investigations and present study show that the
identied minerals and phases in BA include approximately 229
species and groups of species, which are arranged systematically
and alphabetically (Table 3). In contrast, the minerals and phases
found in coal ash are totally about 188 species and groups of species [146] and most of them are listed in Table 11 (based on
[148,150,166,167]). The identied minerals in BA (in decreasing
number of species) belong to the mineral classes: silicates > oxides
and hydroxides > sulphates (plus sulphides, sulphosalts, sulphites
and thiosulphates) > phosphates > carbonates > chlorides (plus
chlorites and chlorates) > nitrates (Table 3). The common phases
found in BAs (in decreasing number of identications) comprise:
(1) Mostly quartz, calcite, sylvite, arcanite, anhydrite, char,
glass, lime, periclase and hematite.
(2) Subordinately portlandite, cristobalite, hydroxylapatite, larnite, albite, Ca phosphates, fairchildite, K carbonate, K feldspars, halite and KCa silicates.
(3) More rarely akermanite, plagioclases, wollastonite, dolomite, apatite, Ca langbeinite, dioxins, furans, gehlenite, K silicates and rutile.
(4) Occasionally glaserite, kalsilite, K phosphates, oldhamite,
amorphous inorganic matter, anorthite, aphthitalite, CaAl
oxides, diopside, ettringite, gypsum, melilite, merwinite,
muscovite, natrite, tridymite; plus a number of uncommon
(accessory) phases (Table 3).
65
(1) Forming (>10%) such as glass, sylvite, calcite, leucite, anorthite, KCa silicate, char and quartz.
(2) Major (110%), namely albite, anhydrite, ankerite, kaolinite,
siderite, cristobalite, arcanite, hematite, illite, lime, Na silicate, fairchildite, hydroxylapatite, merwinite, periclase, Ca
chlorosilicate, diopside, glaserite, K feldspar, larnite, and
portlandite.
(3) Minor (0.11%) such as K silicate, K phosphate and K carbonate; and
(4) Some accessory phases (<0.1% or only traces) according to
their mean contents.
The present study shows that most of the BAs produced at
500 C/2 h (Fig. 6) have a highly crystalline character with limited
occurrence of inorganic amorphous material and organic matter at
this temperature. Only a few individual char particles were recognized by light microscopy in these ashes as black porous particles
particularly encapsulated by silicates. The XRD data reveal the
occurrence of different minerals in the BAs studied (Fig. 6). Most
of them seem to be newly formed minerals in BAs and they belong
to carbonate, sulphate, silicate and phosphate classes. Some of
them are very interesting species from technological and environmental points of view (see Part 2 and [150,151]) because they are
not typical of coal ashes ([148,150,166,167,227] and references
therein). The BC sample thermally treated in air up to 1300 C
(Fig. 4) is just given for an illustration of some phase transformations and formations (see Section 3.1.5), and certain contaminations (mullite and partly quartz) occurring in BA with gradual
increasing of temperatures above 500 C.
The reference investigations and present study reveal that
phases in BA are mostly secondary, to a lesser extent tertiary and
occasionally primary in origin. For example, the mineral species
found in biomass ([2] and references therein) and belonging to
classes such as oxalates, silicates, oxides, hydroxides, sulphates,
sulphites, sulphides, phosphates, carbonates, chlorides, nitrates,
amorphous inorganic matter and others can be primary inorganic
species in BA. On the other hand, various silicates, oxides, hydroxides, carbonates, sulphates, sulphides, sulphosalts, sulphites, thiosulphates, phosphates, chlorides, chlorites, chlorates, nitrates,
oxalates, char, amorphous inorganic matter and glass can be newly
formed secondary phases in BA. Additionally, minerals mostly from
silicate, hydroxide, sulphate and carbonate classes, to a lesser extent phosphates and chlorides, and probably some nitrates can also
have tertiary origin (Table 3 and see Section 3.3 for details). These
observations are similar to those for coal ash (Table 11).
Finally, it can be seen that most of the minerals and phases
identied in coal ashes (Table 11) were also found in BAs (Table 3).
However, many mineral species among CaKMn silicates, CaAl
Mn oxides, KNaCa chlorides and KCaMgNa carbonates, sulphates and phosphates were normally not identied in coal ashes.
The reason for that could be the enrichment of elements such as Ca,
Cl, K, Mg, Mn, Na and P in BAs compared to coal ashes. In contrast,
many Al-, Fe-, Si- and Ti-bearing minerals, typical for coal ashes,
were not identied in BAs probably due to limited contents of
these elements in BAs [1,2].
3.3. Phasemineral composition of biomass ash

In contrast to coal ashes (Table 11), there are not enough data
for the concentration of minerals and phases for different BAs to divide them into forming, major, minor and accessory phases despite
some quantitative determinations by XRD and computer controlled scanning electron microscopy [40,46,55,59,68,84,106]. Nevertheless, some minerals and phases in BAs produced only from
woody biomass, straw and switchgrass can be divided preliminary
and roughly, in decreasing order of concentration, into:
The phase and mineral composition of BA includes various species and groups of species that belong to different mineral classes,
organic phases, organic minerals and other phases identied in
various BAs worldwide (Table 3). A short summary of the mineral
classes and other common phases based on reference investigations and present study is provided below, while the general and
specic phase transformations during biomass combustion are
66
Table 11
Occurrence, abundance and origin of minerals and phases in coal y ashes from 37 power plants of Bulgaria, Greece, Italy, Spain, The Netherlands and Turkey (based on
[148,150,166,167]).
Mineral, phase
Formula
Quantity
Origin
P
Silicates
Amphibole
Andalusite
CaFe aluminosilicate
CaFeMg aluminosilicate
CaFe silicate
CaMn silicate
Celsian
Chloritoid
Chlorite
Cristobalite
FeMg aluminosilicate
Illite-metaillite
Kaolinite-metakaolinite
K feldspars
Larnite
Melilite (akermanite-gehlenite)
Mica
Monticellite
Mullite
Muscovite
Olivine
Opal
Plagioclases
Pyroxene
Quartz
Rankinite
Talc
Tridymite
Vermiculite
Wollastonite
Zeolites
Zircon
Oxides and hydroxides
Alumina
Anatase
BaCa oxyhydroxide
Baddeleyte
Ba hydroxide
Boehmite
Brookite
Brucite
Ce oxide
Chalcophanite
Chromite
Chromspinel
Corundum
Cuprite
Diaspore
Fe spinel
Gibbsite
Hematite
Hercynite
Ilmenite
Jacobcite
Lime
Limonite
Maghemite
Magnesioferrite
Magnetite
Periclase
Portlandite
Pyrolusite
Rutile
Spinel
Tenorite
Ulvospinel
WNbPb oxide
Zincite
Sulphates
Anglesite
NaCa2(Mg, Fe, Al)5(Si, Al)8O22(OH)2

Al2SiO5
BaAl2Si2O8
(Mg, Fe)2Al4Si2O10(OH)4
(Mg, Fe)5Al2Si3O10(OH)8
SiO2
(K,H2O)Al2(Al, Si)Si3O10(OH)2
Al2Si2O5(OH)4
KAlSi3O8
b-Ca2SiO4
Ca2MgSi2O7CaAl(Si, Al)2O7
K, Na, Mg, Fe, Li aluminosilicates
CaMgSiO4
Al6Si2O13
KAl2AlSi3O10(OH, F)2
Mg, Fe, Ni, Mn silicates
SiO2nH2O
NaAlSi3O8CaAl2Si2O8
Mg, Fe, Ca, Mn, Na, Li silicates
SiO2
Ca3Si2O7
Mg3Si4O10(OH)2
SiO2
(Mg, Fe, Al)3(Si, Al)4O10(OH)24H2O
a-Ca3Si3O9
(Ca, Sr, Ba, Na2, K2)Al2Si210O82428H2O
ZrSiO4
c-Al2O3
A
A
A
A
A
A
A
A
AMi
AM
A
AM
AM
AM
AM
AM
AM
AM
MiF
AM
AMi
A
MiM
AMi
MF
AMi
A
AM
A
AM
A
A
ZnO
A
A
A
A
A
AMi
A
AMi
A
A
A
A
AM
A
AMi
A
AMi
MiM
A
A
A
AM
AMi
AMi
AMi
MiM
AMi
AM
A
A
AMi
A
A
A
A
PbSO4
TiO2
ZrO2
c-AlOOH
TiO2
Mg(OH)2
ZnMn3O7.3H2O
FeCr2O4
CrFe2O4
Al2O3
Cu2O
a-AlOOH
Mg(Al, Fe)2O4
Al(OH)3
a-Fe2O3
FeAl2O4
FeTiO3
MnFe2O4
CaO
Fe products
v-Fe2O3
MgFe2O4
FeFe2O4
MgO
Ca(OH)2
b-MnO2
TiO2
MgAl2O4
CuO
TiFe2O4

67

Table 11 (continued)
Mineral, phase
Anhydrite
Alunite
Barite
Bassanite
Ettringite
Fe sulphates
Gypsum
Jarosite
Mg sulphates
NaK sulphates
Formula
CaSO4
KAl3(SO4)2(OH)6
BaSO4
CaSO40.5H2O
Ca6Al2(SO4)3(OH)1226H2O
CaSO42H2O
KFe3(SO4)2(OH)6
Quantity
Origin
P
AF
A
AMi
A
AM

AMi
AF
AM
AMi
AMi

Carbonates
Ankerite
Calcite
Cerussite
Dolomite
Manganocalcite
Witherite
Ca(Mg, Fe)(CO3)2
CaCO3
PbCO3
CaMg(CO3)2
CaMn(CO3)2
BaCO3
AM
AM
A
AM
A
A

Phosphates
Apatite
Goyazite
Monazite
Ningyoite
Svanbergite
Vivianite
Ca(PO4)3(Cl, F, OH)
Al2Sr(PO4)2(OH)5H2O
(Ce, La, Y, Th) (PO)4
CaU(PO4)22H2O
SrAl3(PO4)(SO4)(OH)6
Fe3(PO4)28H2O
A
A
A
A
A
A

Cu2S
Fe1xS
A
A
A
CaWO4
NaCl
Ca, R, Na(C2O4)nnH2O
Sulphides and sulphosalts

Chalcocite
PbSb sulphosalt
Pyrrhotite
Tungstates
Scheelite
Carbides
Fe carbide
Native elements
Graphite
Chlorides
Halite
Organic minerals
CaKNa oxalate
Others
Char
Glass
AF
F

Abbreviations: F, forming (>10%); M, major (110%); Mi, minor (0.11%); A, accessory (<0.1%); P, primary; S, secondary; T, tertiary; , dominant; , subordinate.
beyond the subject of the present study and they will be characterized in a further publication.
3.3.1. Silicates
The numerous silicates identied in BA are listed in Table 3.
They can be mostly secondary, to a lesser extent primary, and occasionally tertiary phases in BA. These minerals have both detrital
and authigenic occurrence in/on plants because:
(1) Quartz, cristobalite, feldspars, clay and mica minerals, and
some pyroxenes and olivines are typical soil minerals
[24,25,35,56,57,62,68,98,105,228] and they can have some
detrital uptake from the soil during plant growth.
(2) Opal is a characteristic authigenic mineral in plants and originates from syngenetic and epigenetic evaporation and precipitation of water, namely mineralized aqueous solution
enriched in non-charged silicic acid ([2] and references
therein).
Hence, some silicates can be primary phases in BA due to their
possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Additionally, some technogenic silicate impurities as additives or contaminants in semi-biomass (clay minerals, zeolites, talc and other
silicates in Table 3) generated from processing of natural biomass
can also be primary as a result of their occurrence as unaltered
minerals in BA [37,38,45]. However, the secondary silicates are
dominant in BA and these newly formed phases originate from
the alteration of pre-existing silicates, melt crystallization and
mostly from the complex reactions among silica and oxyhydroxides of Al, Ba, Ca, Cd, Fe, K, Mg, Mn, Na, Sr and Ti (Table 3) generated commonly from the decomposition of organic matter,
oxalates, carbonates, phosphates, sulphates, chlorides and nitrates
during biomass combustion. For example, crystallization of various
newly formed silicates (grains and crystals with size between 1 lm
and 1 mm) within the glass matrix originated from the melt and in
wollastonite matrix was observed in some BAs [28,30,48]. The origin of these secondary silicates in BA is similar to that in coal ash
and their formation mechanisms have been described in detail earlier ([163,164] and references therein). Finally, the tertiary silicates
can include minerals containing water molecules and/or hydroxyl
groups (for example, afwillite, Ca silicate hydrate, gismondite,
68
some clay minerals and zeolites), which are a result of hydration

and hydroxylation of other less stable silicates by water and moisture in the air during transport and storage of BA [24,60,65].
3.3.2. Oxides and hydroxides
The various oxides and hydroxides found in BA are listed in Table 3. They can be mostly secondary, to a lesser extent tertiary, and
occasionally primary phases in BA. These minerals have commonly
detrital and occasionally authigenic accessory occurrence in/on
plants because:
(1) Fe, Al and Ti oxyhydroxides are typical soil minerals
[62,98,228] and they can have some relatively low detrital
uptake from the soil during plant growth [43].
(2) Some authigenic hydroxides in plants may originate from
syngenetic and epigenetic evaporation and precipitation of
mineralized aqueous solution enriched in different cations
and hydroxide anion ([2] and references therein).
Hence, some oxyhydroxides can be primary phases in BA due to
their possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Additionally, the occurrence of some technogenic Fe-, Al-, Mg-, Ca- and
Ti-bearing oxyhydroxides (Table 3) in semi-biomass as impurities
(additives or contaminants) generated from processing of natural
biomass can also be primary as a result of their presence as unaltered minerals in BA [37]. However, the secondary oxyhydroxides
of Al, Ca, Cd, Cr, Fe, K, Mg, Mn, Na, Pb, Pd, Ti and Zn (Table 3) are
dominant in BA and these newly formed phases originate mostly
from the decomposition and oxidation of organic matter, oxalates,
carbonates, phosphates, sulphates, chlorides and nitrates, and, to a
lesser extent, melt crystallization during biomass combustion. The
origin of these secondary oxyhydroxides in BA is similar to that in
coal ash and their formation mechanisms have been described in
detail earlier excluding the phases containing some trace elements
([163,164] and references therein). Finally, the tertiary hydroxides
can include minerals containing hydroxyl groups and water molecules (for example, gibbsite, goethite, portlandite, brucite, hydrocalumite and K and Na hydroxides), which are a result of
hydration and hydroxylation of other less stable oxides by water
and moisture in the air during transport and storage of BA
[24,34,57,60,62,89].
3.3.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates
The various sulphates identied in BA are listed in Table 3. They
can be mostly secondary, to a lesser extent tertiary, and occasionally primary phases in BA, which is identical to oxyhydroxides. Sulphates are highly mobile during weathering and they are not
typical soil minerals [228]. These minerals have authigenic occurrence in plants because they originate from syngenetic and epigenetic evaporation and precipitation of mineralized aqueous
solution enriched in different cations and sulphate anion, as well
as probably sulphide anion ([2] and references therein). Hence,
some sulphates can be primary phases in BA due to their possible
presence as unchanged relics having relatively moderate to high
decomposition and/or melting temperatures during heating. Additionally, the occurrence of some technogenic Al, Ca and Fe sulphates (Table 3) in plants from fertilizers and in semi-biomass as
impurities (additives or contaminants) generated from processing
of natural biomass can also be primary as a result of their presence
as unaltered minerals in BA [38]. However, the secondary sulphates of Al, Ca, K, Mg and Na (Table 3) are dominant in BA and
these newly formed phases are commonly attributed to interaction
between acidic SOX (SO2 and SO3) gases and oxides of the above
elements generated mostly from organic matter during biomass
combustion. The origin of these secondary sulphates is similar to
that in coal ash and their formation mechanisms have been described in detail earlier ([163,164] and references therein). Finally,
the tertiary sulphates can include minerals containing water molecules and/or hydroxyl groups (for example, gypsum, bassanite,
ettringite, picromerite, syngenite), which are a result of hydration
and hydroxylation of other less stable sulphates by water and
moisture in the air during transport and storage of BA [24,57,65].
The less stable sulphides, sulphosalts, sulphites and thiosulphates
(Table 3) are not characteristic phases of BA in contrast to sulphates, and their accessory occurrence can be a result of some
reducing and unstable conditions in the system during biomass
combustion. For example, this statement is evidenced by the association of sulphides with char in BA [112].
3.3.4. Phosphates
The various phosphates found in BA are listed in Table 3. They
can be mostly secondary, to a lesser extent primary, and occasionally tertiary phases in BA, which is identical to silicates. These minerals have both detrital and authigenic occurrence in/on plants
because:
(1) Some phosphates (such as the group of apatite) are typical
soil minerals [228] and they can have some relatively low
detrital uptake from the soil during plant growth; and
(2) Phosphates are characteristic authigenic minerals in plants
and animals and originate from syngenetic and epigenetic
evaporation and precipitation of mineralized aqueous solution enriched in different cations and phosphate and hydrogen phosphate anions ([2] and references therein).
Hence, some phosphates can be primary phases in BA due to
their possible presence as unchanged relics having relatively high
decomposition and/or melting temperatures during heating. Additionally, the occurrence of some technogenic phosphates (Table 3)
in plants from fertilizers and in semi-biomass as impurities (additives or contaminants) generated from processing of natural biomass can also be primary as a result of their presence as
unaltered minerals in BA [24,38,41,42,45,62,104]. However, the
secondary phosphates of Al, Ca, Fe, K, Mg, Na and Zn (Table 3)
are dominant in BA and these newly formed phases are attributed
to interaction between oxides of the above-listed elements and P
generated mostly from organic matter, as well as melt crystallization during biomass combustion. For example, evidence of apatite
crystallization within the SiK glass formed from melt was observed in BA [48]. The origin of these secondary phosphates is
probably similar to that in coal ash and this has been suggested
elsewhere [94]. Finally, the tertiary phosphates can include minerals containing water molecules and/or hydroxyl groups (for example, hydroxylapatite and K pyrophosphate hydrate), which are a
result of hydration and hydroxylation of other less stable phosphates by water and moisture in the air during transport and storage of BA [57]. The less stable pyrophosphates (Table 3) are not
characteristic phases of BA in contrast to phosphates, and their
accessory occurrence could be a result of some unstable conditions
in the system during biomass combustion.
3.3.5. Carbonates and bicarbonates
The various carbonates and bicarbonates identied in BA are
listed in Table 3. They can be mostly secondary, to a lesser extent
tertiary, and occasionally primary phases in BA, which is identical
to oxyhydroxides and sulphates. These minerals have both detrital
and authigenic occurrence in/on plants because carbonates are:
(1) Typical minerals for some soils [62,98,228] and they can
have some relatively low detrital uptake from the soil during
plant growth.
(2) Characteristic authigenic minerals in plants and animals and

originate from syngenetic and epigenetic evaporation and
precipitation of mineralized aqueous solution enriched in
different cations and carbonate, hydrocarbonate and hydrobicarbonate anions ([2] and references therein).
Hence, some carbonates can be primary phases in BA due to
their possible presence as unchanged relics despite their relatively
moderate decomposition and/or melting temperatures during
heating. Additionally, the occurrence of some technogenic carbonates in semi-biomass as impurities (additives or contaminants)
generated from processing of natural biomass can also be primary
as a result of their presence as unaltered minerals in BA (Table 3).
However, the secondary carbonates of Al, Ca, Cr, Fe, K, Mg and Na
(Table 3) are normally dominant in BA and these newly formed
phases originate from the decomposition and oxidation of organic
matter, oxalates and carbonates and subsequent carbonation (and
recarbonation) of the secondary oxyhydroxides during biomass
combustion [65,94,107]. Hence, the origin of these secondary carbonates in BA is similar to that in coal ash and their formation
mechanisms have been described in detail for some carbonates
([163,164] and references therein). On the other hand, tertiary carbonates can be formed from secondary Ca and Mg hydroxides during transport and storage of BA due to reactions of the former
minerals with CO2 occurring in air and water [24,57,60,65]. Finally,
other tertiary carbonates can also include minerals containing
water molecules and/or hydroxyl groups (for example, arterite,
baylissite, hydrocalcite, hydrotalcite, nesquehonite, paraalumohydrokalcit), which are a result of hydration and hydroxylation of
other less stable carbonates by water and moisture in the air during transport and storage of BA.
3.3.6. Chlorides, chlorites and chlorates
The chlorides identied in BA are listed in Table 3. They can be
mostly secondary, to a lesser extent primary, and occasionally tertiary phases in BA, which is identical to silicates and phosphates.
Chlorides are highly mobile during weathering and they are not
typical soil minerals [228], similar to sulphates. These minerals
have authigenic occurrence in plants because they originate from
syngenetic and epigenetic evaporation and precipitation of mineralized aqueous solution enriched in different cations and chloride
anion ([2] and references therein). Hence, some chlorides can be
primary phases in BA due to their possible presence as unchanged
relics despite their relatively low to moderate decomposition and/
or melting temperatures during heating. Additionally, the occurrence of some technogenic chlorides in plants from fertilizers and
in semi-biomass as impurities (additives or contaminants) generated from processing of natural biomass can also be primary as a
result of their presence as unaltered minerals in BA (Table 3).
The secondary chlorides of Ca, Cd, K, Na, Pb and Zn (Table 3) are
dominant in BA and these newly formed phases are commonly
attributed to interaction between Cl gases and the above elements
(generated mostly from organic matter) during biomass combustion. The origin of these secondary chlorides is probably similar
to that in coal ash. Finally, the tertiary chlorides can include minerals containing water molecules and/or hydroxyl groups (for
example, Ca chlorite hydrate, Ca hydroxylchloride), which are a result of hydration and hydroxylation of other less stable chlorides
by water and moisture in the air during transport and storage of
BA. The less stable chlorites and chlorates (Table 3) are not characteristic phases of BA in contrast to chlorides, and their accessory
occurrence can be a result of some unstable conditions in the system during biomass combustion. For example, potassium forms
perchlorates during low-temperature oxidation (100250 C) and
these compounds decompose between 200700 C releasing Cl
[68].
69
3.3.7. Nitrates
The nitrates identied in BA are listed in Table 3. They can be
secondary and probably primary and tertiary phases in BA; however, the available information for them is very limited. Nitrates
are highly mobile during weathering and they are not typical soil
minerals [228], similar to sulphates and chlorides. These minerals
have authigenic occurrence in plants because they originate from
syngenetic and epigenetic evaporation and precipitation of mineralized aqueous solution enriched in different cations and nitrate
anion ([2] and references therein). Hence, some nitrates may be
primary phases in BA due to their probable presence as unchanged
relics despite their relatively low decomposition and/or melting
temperatures during heating. Additionally, the occurrence of some
technogenic nitrates in plants from fertilizers and in semi-biomass
as impurities (additives or contaminants) generated from processing of natural biomass may also be primary as a result of their presence as unaltered minerals in BA (Table 3). The secondary nitrate of
K (Table 3) is probably dominant in BA and this newly formed
phase can be attributed to interactions between acidic NOX (NO
and NO2) gases and K (generated mostly from organic matter) during biomass combustion. The origin of this secondary nitrate is
probably similar to that in coal ash [94]. For example, potassium
forms nitrates during low-temperature oxidation (100250 C)
and these compounds decompose between 200 and 700 C releasing N [68]. Finally, the tertiary nitrates may include minerals precipitated from water solutions (enriched in nitrate anion) and
generated during transport and storage of BA.
3.3.8. Glass
Glass is mostly newly formed secondary phase in BA resulted
from fusion of inorganic material in biomass and abrupt cooling
of the melt produced during combustion. Some unchanged glass
particles may also be primary in BA if there is pre-existing detrital
(from volcanic rocks in soil and their uptake) and technogenic
(impurities from additives or contaminants) occurrence of glass
with relatively high melting temperatures in biomass and semibiomass, respectively. It was found that glass in BA contains primarily Si, K, Ca and Na, and, to a lesser extent, Mg, S, P, Fe, Mn
and Al [30,33,48,69]. It forms rock-like, ribbon-like, hair-like and
other morphological types [69]. Glass agglomerates also occur in
BA, composed of different sintered or melted ash particles bound
by glassy materials [57,69]. It was identied that some high silica
BAs (especially rice straw ash) produce highly vesicular glass products from bubble formation and expansion. These products occasionally form hollow spherical particles of 510 lm in diameter,
which entrap gases [28,53,102]. This is similar to coal ash cenospheres [229]. In contrast to silica enriched BA, high Ca wood BA
normally produces massive glass beads without quench crystals
and vesicles [28,53]. The observations above are identical or similar to those identied for various glass morphologies in coal ash
[148,167].
3.3.9. Other inorganic phases
The other inorganic phases identied in BA are listed in Table 3.
The newly formed amorphous (non-glass) inorganic material represents particles composed of non-fused phases and they were
identied in BA produced from different biomass varieties
[24,35,48,53,65,74,86,94]. It is well known, that phases such as
clay, mica and silica minerals, zeolites and some hydroxides, sulphates and phosphates lose their crystallization water at 300
1100 C, resulting in structural collapse and consequent amorphization in this temperature range ([151,164] and references therein). For example, the presence of amorphous sulphate phases [74],
poorly crystallised hydrohylapatite [56] and non-crystalline needle-shaped silica grains or rounded to irregular shaped grains composed mostly of Si, K and Ca [53] were observed in some BAs.
70
Additionally, the formation of hydrated silicate phases and portlandite with amorphous, disordered or poorly crystallised structures during hydration of BA is also common [24,65].
Finally, different metallic alloys and pure metals are typical
minor and accessory phases in municipal solid waste ashes
[27,38], other industrial ashes [109], and even some plants [108].
Hence, these metallic alloys and pure metals can occur as unchanged relics or impurities (additives or contaminants) in BA if
they have relatively high melting temperatures. The presence of
some unusual phases such as KMo selenide [100] and margaritasite ((Cs,K,H3O)2(UO2)2V2O8(H2O)) [73] in ashes produced from
incomplete combustion of oil palm biomass waste (bers from
empty fruit bunches) and rice husks, respectively, has also been
reported.
3.3.10. Organic phases
The organic phases identied in BA are listed in Table 3. They
include mostly secondary semi-coked and coked char particles
and associated with them other minor organic phases in BA originated from incomplete biomass combustion. Additionally, the
presence of some technogenic organic phases in semi-biomass as
impurities (additives or contaminants) generated from processing
of natural biomass can also occur in BA. The char contents in BA
are highly variable (0.379%), but the most common values are
in the range 120% [35,47,63,73,76,97,114,129,136]. The char particles have various morphologies (Table 1), but the original textures and structures of biomass are often maintained in char
particles [47,123,230232]. It was found that the coarser grain
fractions of BA normally contain increased contents of unburned
matter [47,133,134]. An association of organic pollutant species
(polychlorinated dioxins and furans and polycyclinc aromatic
hydrocarbons) with char when the unburned organic levels in BA
are high is also possible [14,95]. Finally, Na cyanate is formed from
biomass combustion; however, cyanate is only stable under reducing conditions and decomposes to other alkali salts and gaseous N
compounds at oxidizing conditions [128].
3.3.11. Organic minerals
Weddelite (Ca oxalate dihydrate), whewellite (Ca oxalate
monohydrate) and dehydrated whewellite were identied in
low-temperature BA, but not in high-temperature BA (Table 3).
Oxalates are minerals, but they are specied to a special group
because they are organic species, which is one of the exceptions
in a mineralogical sense [228]. They can be secondary and probably primary phases in BA. Oxalates are typical authigenic minerals
in plants because they originate from syngenetic and epigenetic
evaporation and precipitation of mineralized aqueous solution
enriched in different cations and oxalate anion ([2] and references
therein). Hence, some oxalates may be primary phases in BA due
to their possible presence as unchanged relics despite their
relatively low to moderate decomposition temperatures during
heating. Additionally, the occurrence of some technogenic oxalates in semi-biomass as impurities generated from processing
of natural biomass may also be primary as a result of their
presence as unaltered minerals in BA (Table 3). However, the
secondary oxalates of Ca, K, Mg, Mn and Na are probably dominant in BA (Table 3 and [2]) and these newly formed phases
may be a result of decomposition of organic matter under some
unstable and lower temperature conditions in the system during
biomass combustion [94].
3.4. Chemical and phasemineral classications of biomass and
biomass ash and their potential applications
The characterization of phasemineral and chemical composition of biomass and BA has a key importance in both fundamental
and applied aspects of biomass fuels and their combustion products, similar to coal and coal ash [150,151,170]. Further, the chemical and phasemineral classications of biomass and BA can assist
directly or indirectly in:
(1) Establishment of a uniform nomenclature and standards.
(2) Characterization of composition and prediction of
properties.
(3) Elucidation of the behaviour of organic and inorganic matter
during processing.
(4) Identication of appropriate or potential modes of
utilization.
(5) Prediction, assessment, reduction or elimination of technological, ecological and health problems or benets such as:
Economically
valuable
or
environmentally
hazardous
components.
Innovative (effective, muticomponent, wasteless) and sustainable utilization.
Biological, physical, chemical and thermo-chemical performance in industrial installations.
Global and local environmental contamination of the air,
water, soil and plants by toxic and potentially toxic compounds
[2].
It has been evidently demonstrated that the inorganic composition of biomass and BA is highly variable [1,2]. Therefore, the
assignment of various biomass varieties to different inorganic
types and sub-types could have primary signicance when predicting the behaviour of a particular fuel during processing and potential applications of biomass conversion (combustion, pyrolysis and
gasication) products. Therefore, some chemical and phase approaches for initial and preliminary classication and prediction
purposes related to biomass and BA has been introduced or suggested recently (Figs. 1 and 7 and others in [1,2]). They are similar
to those that have been earlier applied for coal and coal ash
[150,151,170]).
There is a big advantage when the biomass and BA classication
systems are based on the identication and implementation of signicant relationships between elemental concentrations, combined chemical and phasemineral associations and especially on
an application of genetic approaches for specication of the phases.
In this case the reasons for different problems or benets during
biomass processing can be systematically identied. Therefore,
the specied oxide associations based on the correlation analysis
in BA [1] are also informative for the preferable occurrence and
possible origin of inorganic elements in BA and this is demonstrated below. For instance, the chemical classication of BAs
(Fig. 1) is extended (Fig. 7) including the dominant phasemineral
composition of BAs (Table 3) as:
(1) The upper corner (SiO2 + Al2O3 + Fe2O3 + Na2O + TiO2) in
Fig. 7 mostly represents the occurrence of glass, silicates
and oxyhydroxides of these elements in BA.
(2) The left corner (CaO + MgO + MnO) in Fig. 7 commonly
includes carbonates, oxyhydroxides, glass, silicates and
some phosphates and sulphates of such elements in BA.
(3) The right corner (K2O + P2O5 + SO3 + Cl2O, as N also belongs
to this association, see [1]) in Fig. 7 normally represents
phosphates, sulphates, chlorides, glass and some silicates
and carbonates of these elements in BA. Certainly, some of
the phases or minerals have mixed contributions to the different corners because of their complex composition.
The above three systematic associations related to the occurrence, content and origin of elements and phases divide BAs
(Fig. 7) to:
71
WWB - Wood and woody biomass

HAB - Herbaceous and agricultural biomass
HAG - Herbaceous and agricultural grass
HAS - Herbaceous and agricultural straw
HAR - Herbaceous and agricultural residue
AB - Animal biomass
MB - Mixture of biomass
CB - Contaminated biomass
AVB - All varieties of biomass
P - Peat
L - Lignite
S - Sub-bituminous coal
B - Bituminous coal
A - Algae
Fig. 7. Position areas of 86 biomass varieties and 38 solid fossil fuels in the chemical classication system of biomass ash based on [1,2,170], wt.%.
Four ash types (S, C, K and CK).

Six ash sub-types (S-HA, S-MA, C-MA, C-LA, K-MA and
K-LA).
Additionally, the concept of dividing inorganic matter into: natural (authigenic, detrital) and technogenic classes for biomass [2];
and primary, secondary and tertiary classes for BA in the present
work; has also both fundamental and applied importance. For
example:
(1) The authigenic minerals in biomass are opal, oxalates, carbonates, phosphates, sulphates, chlorides and nitrates (characteristic of inorganic C, K and CK types of biomass).
Such minerals are normally highly mobile (water-soluble)
and reactive, and with low decomposition or melting temperatures. Therefore, they can be responsible for enhanced
leaching behaviour, low-temperature transformations, partitioning behaviour and emission (or capture) of many volatile
elements and hazardous components, corrosion, agglomeration, deposits formation, slagging, fouling, bed deuidization
and composition of residues during biomass combustion [2].
Some of these authigenic minerals can occur as primary
(unchanged) phases in BA, but they commonly form secondary and tertiary Ca-, K-, Mg-, Na- and Mn-bearing carbonates, oxyhydroxides, phosphates, sulphates, chlorides, glass
and some silicates in BA (Fig. 7) as a result of subsequent
reactions with: detrital minerals; inorganic and organic
components released from organic matter during biomass
combustion; and with air and moisture during BA storage.
(2) The detrital minerals in biomass are silicates and oxyhydroxides, excluding opal (typical of inorganic S type of biomass). Such minerals are commonly stable, less mobile
(water-insoluble), less reactive and with high-melting tem-
peratures during combustion. Therefore, they can be important for enhanced abrasion-erosion, formation of some lowtemperature eutectics, partitioning element behaviour and
for decreasing combustion efciency and increasing operating costs for the handling of such inert material during biomass combustion [2]. Many of these detrital minerals can
occur as primary (unchanged) phases in BA, but they mostly
form secondary Si-, Al-, Fe-, Na- and Ti-bearing glass, silicates and oxyhydroxides (Fig. 7) due to subsequent reactions
with: authigenic minerals; inorganic and organic components released from organic matter during biomass combustion; and with air and moisture during BA storage (similar to
authigenic minerals).
(3) The technogenic minerals in biomass include various
anthropogenic species with highly variable properties and
behaviour (characteristic for different inorganic types). They
can also be responsible for many of the above listed problems plus enhanced pollution by trace elements because
most semi-biomass fuels contain high levels of such elements [2]. The technogenic minerals in biomass can also
be primary, secondary and tertiary phases in BA.
Furthermore, it should be stated that biomass fuels with similar bulk chemical composition may behave quite differently and
may generate distinctly different solid products during biomass
conversion. This is due to different modes of element occurrence
in biomass and BA. For example, the organic phases and mineral
classes, groups and species occurring in biomass [2] and BA
(Table 3) have different behaviour during processing. Hence,
their actual identication, quantication and associations in a
specic biomass and BA can be used to predict the behaviour
of fuel during conversion and potential applications of BA.
Additionally, the knowledge of phase, mineral and element
72
occurrences in biomass and their transformations during biomass thermal treatment is important for determining formation
mechanism of BA, as also demonstrated for coal and coal ash
[150,151,163,164,170].
Finally, it is suggested that the inorganic chemical types and
sub-types classied [1] and the specied origin of inorganic matter
in biomass [2] and BA (as Fig. 7) may also play a leading role in
many technological and environmental problems, similar to coal
and coal ash [150,151,170]). Therefore, the specied inorganic
types and sub-types, and genetic mineral classes, as well as structural organic types of biomass ([1,2]; Tables 2, 4, 5, 8 and 9; and
Figs. 17) will be used for some prediction of potential utilization,
technological and ecological advantages and challenges related to
BA. These topics will be discussed in Part 2.
4. Conclusions
Some conclusions based on the present overview of the phase
mineral and chemical composition of biomass ash (BA) can be
made:
(1) BA is the solid residue that results from the combustion of
biomass. It is a complex inorganicorganic mixture with
polycomponent, heterogeneous and variable composition,
containing intimately associated solid, liquid and gaseous
phases with different origin. The phasemineral composition
of BA includes (1) mostly inorganic matter composed of noncrystalline (amorphous) and crystalline to semi-crystalline
(mineral) constituents; (2) subordinately organic matter
consisting of char and organic minerals; and (3) some uid
matter comprising moisture and gas and gasliquid inclusions associated with both inorganic and organic matter.
(2) The chemical elements present in BA (in decreasing order of
abundance) are commonly O > Ca > K > Si > Mg > Al >
Fe > P > Na > S > Mn > Ti, plus some Cl, C, H, N and trace elements. BA from natural biomass is commonly enriched in
Mn > K > P > Cl > Ca > Na > Mg and depleted in Al > Ti >
Fe > Si > S in comparison with coal ash. Trace elements such
as B > Au > Cd > (Cr, Mn) > Ag > Zn > (Be, Cu, Se) > Ni > Rb in
different BAs can show higher contents (224 times) than
the respective worldwide average values for coal ashes.
(3) The minerals and phases found in BAs (229 identied)
include more species and groups of species in comparison
with coal ashes (188 identied). The minerals identied in
BAs (in decreasing number of mineral species) belong to
the mineral classes: silicates > oxides and hydroxides >
sulphates (plus sulphides, sulphosalts, sulphites and thiosulphates) > phosphates > carbonates > chlorides (plus chlorites and chlorates) > nitrates. The common phases found
in BAs (in decreasing number of identications) comprise:
(1) mostly quartz, calcite, sylvite, arcanite, anhydrite, char,
glass, lime, periclase and hematite and (2) subordinately
portlandite, cristobalite, hydroxylapatite, larnite, albite, Ca
phosphates, fairchildite, K carbonate, K feldspars, halite
and KCa silicates.
(4) The minerals and phases in BA can be divided into: (1) forming (>10%); (2) major (110%); (3) minor (0.11%); and (4)
accessory (<0.1%); based on their contents. The forming
and major phases (in decreasing order of abundance) in
BAs include glass, sylvite, calcite, leucite, anorthite, KCa silicate, char, quartz, albite, anhydrite, ankerite, kaolinite, siderite, cristobalite, arcanite, hematite, illite, lime, Na silicate,
fairchildite, hydroxylapatite, merwinite, periclase, Ca chlorosilicate, diopside, glaserite, K feldspar, larnite and
portlandite.
(5) BA is composed of original or newly formed inorganic and

organic solid phases generated from natural (authigenic
and detrital) and technogenic inorganic, organic and uid
matter during biomass combustion. Therefore, the phases
and minerals in BA can be classied in origin as: (1) primary,
namely pre-existing or original minerals and phases in biomass that have undergone no phase transformations during
combustion; (2) secondary such as new phases formed during combustion process; and (3) tertiary, namely new minerals or phases formed during transport and storage of BA.
The phases found in BA are mostly secondary, to a lesser
extent tertiary and occasionally primary in origin.
(6) Most of the minerals and phases identied in coal ashes
were also found in BAs. However, many mineral species
among CaKMn silicates, CaAlMn oxides, KNaCa chlorides and KCaMgNa carbonates, sulphates and phosphates identied in BA were normally not found in coal
ashes. The reason for that could be the enrichment of elements such as Ca, Cl, K, Mg, Mn, Na and P in BAs compared
to coal ashes. In contrast, many Al-, Fe-, Si- and Ti-bearing
minerals, typical for coal ashes, were not indentied in BAs
probably due to limited contents of these elements in BAs.
(7) The ash yield from biomass (animal > aquatic > contaminated > herbaceous and agricultural > wood and woody) is
normally much lower than the ash yield from coal. Natural
biomass commonly enriched in hemicellulose, water-soluble salts and silicic acid (authigenic phosphates, sulphates,
chlorides, nitrates and opal) tends to produce higher ash
yields. The unusually high ash yields of biomass are commonly an indication of increased amounts of contamination
with detrital or technogenic origin.
(8) Organic matter of different biomass varieties tends to show
similar combustion behaviour, whereas the inorganic matter
of these biomass varieties has a tendency to reveal very variable performance during burning. The ash-fusion temperatures of biomass are more variable than of coal and they
are normally lower. The preliminary observations also indicate that the thermal behaviour of different biomass ashes
tends to be similar among the inorganic S, C, K and
CK types and probably some sub-types specied.
(9) The content of water-soluble fraction in BA is high and can
be up to 61.0%, while the values of this characteristic for coal
ashes are much less, namely 0.27.2% (mean 1.6%). The pH
values of BAs vary in the range 4.513.4 (mean about
10.7), while for coal ashes these values are in more narrow
range, namely 6.212.5 (mean 10.0). The water-soluble elements leached from BAs are commonly Cl > S > K > Na >
Sr > Ni > Mn > Cd > Cr > Zn > Co > Si > Mo > Li > (Mg, Pb) > Ca >
Cu > Ba > P > Se > Sb > Al > Fe > (Br, Hg) > (As, B, Sn, Ti, V).
The water-soluble phases in BA mostly include phases of
alkali and alkaline earth elements such as: (1) highly soluble
chlorides (sylvite, halite), sulphates (arcanite, syngenite,
ettringite, gypsum), oxides (lime), hydroxides (portlandite),
nitrates, carbonates and bicarbonates; (2) certain less soluble carbonates (calcite) and phosphates (phosphorites);
and (3) some slightly soluble phosphates (apatite) and silicates (Ca silicates, feldspars).
(10) Sequential chemical fractionation is mostly used to distinguish the speciation of elements in BAs. However, this indirect, rather unselective and maybe unreliable procedure
cannot be applied to identify the actual modes of element
occurrence in a multicomponent system such as biomass
ash and the interpretation should always be approached
with much caution. In preference, other direct methods
should be used for such a purpose.
(11) The inorganic composition of biomass and BA is highly variable and the assignment of various biomass varieties to different inorganic types and sub-types could have primary
importance when predicting the behaviour of a particular
fuel during processing and potential applications of biomass
conversion (combustion, pyrolysis and gasication)
products.
(12) There is a big advantage when the biomass and BA classication systems are based on the identication and implementation of signicant relationships between elemental
concentrations, combined chemical and phasemineral
associations and especially on an application of genetic
approaches for specication of the phases. In this case the
reasons for different problems or benets during biomass
processing can be systematically identied.
(13) Certain major associations related to the occurrence, content
and origin of elements and phases were identied in the BA
system and they include: (1) SiAlFeNaTi (mostly glass,
silicates and oxyhydroxides); (2) CaMgMn (commonly
carbonates, oxyhydroxides, glass, silicates and some phosphates and sulphates); and (3) KPSCl (normally phosphates, sulphates, chlorides, glass and some silicates and
carbonates). These associations were applied for classication of BAs to four types and six sub-types. Such systematic
relationships have a key importance in both fundamental
and applied aspects, namely their potential applications for
classications and indicator purposes connected with innovative and sustainable processing of BA.
The potential utilization, technological and ecological advantages and challenges related to BA using the above classication approach are described in Part 2 of the present work.
Acknowledgements
The present work was carried out in part within the European
Commissions research programme and in part within the research
programme of the Bulgarian Academy of Sciences. Stanislav Vassilev would like to express his gratitude to the Joint Research Centre
(European Commission) for the possibility to perform studies at
the Institute for Energy and Transport (Petten, The Netherlands)
as a Detached National Expert.
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Fuel 105 (2013) 4076

Contents lists available at SciVerse ScienceDirect

An overview of the composition and application of biomass ash. Part 1.

S.V. Vassilev et al. / Fuel 105 (2013) 4076

low-temperature ash (100250 C)

S.V. Vassilev et al. / Fuel 105 (2013) 4076

1.1. General considerations about biomass composition

State and type of constituent

Phase, mineral and particle morphology

Solid, crystalline (mineral)

Fluid, liquid, gas

Original phases or minerals that have undergone no phase transformations during

Before and during plant

During transport and

S.V. Vassilev et al. / Fuel 105 (2013) 4076

products. The composition of semi-biomass is more complex

S.V. Vassilev et al. / Fuel 105 (2013) 4076

S.V. Vassilev et al. / Fuel 105 (2013) 4076

[13,33,47,49,53, present study]

1.3. Sulphates, sulphides, sulphosalts, sulphites and thiosulphates

S.V. Vassilev et al. / Fuel 105 (2013) 4076

Compounds with sulphite anion

Ca(PO4)3(Cl, F, OH, CO3) or

1.5. Carbonates and bicarbonates

1.6. Chlorides, chlorites and chlorates

S.V. Vassilev et al. / Fuel 105 (2013) 4076

1.9. Other inorganic phases

[24,35c,48,53,65,86,94,111, present study]

Hydrated or leached ash.

otype groups and macerals; and which are well recognized

S.V. Vassilev et al. / Fuel 105 (2013) 4076

of occurrence of elements in a multicomponent system.

The above listed problems show that additional, systematic and

S.V. Vassilev et al. / Fuel 105 (2013) 4076

Size reduction (mm)

The thermal experiments include a gradual heating of HTAs

RH has a uid ash-fusion temperature higher than 1500 C. Initial

S.V. Vassilev et al. / Fuel 105 (2013) 4076

S.V. Vassilev et al. / Fuel 105 (2013) 4076

3. Results and discussion

(3) Tertiary, namely new minerals or phases formed during

S.V. Vassilev et al. / Fuel 105 (2013) 4076

(1) Biomass resource (type of biomass, plant species or part of

S.V. Vassilev et al. / Fuel 105 (2013) 4076

2. Herbaceous and agricultural biomass (HAB)

2.1. Grasses (HAG)

2.2. Straws (HAS)

2.3. Other residues (HAR)

3. Animal biomass (AB)

4. Mixture of biomass (MB)

5. Contaminated biomass (CB)

All varieties of biomass (AVB)

1. Wood and woody biomass (WWB)

the late winter [131]. Additionally, grass produced on a clay soil

11001500 C are 759% lower than those produced at 500 C,

S.V. Vassilev et al. / Fuel 105 (2013) 4076

Chalcophile elements (metals and semi-metals)

Note: The mineralogical classication of elements [173] was used.

(1) Positively and signicantly (at 95% condence level) with

mass varieties belonging to the specied inorganic biomass types

3.1.5. Formation and behaviour

Finally, it should be stated that the abnormally high ash yields

3.1.4. Correlation and association

Four ash types (S, C, K and CK).